Wave function analysis at DLPNO-CCSD(T)

saeed_E · 2026-06-16 04:52:52

Dear Tian,
In the Multiwfn manual, I found:
"Here I illustrate how to make Multiwfn able to analyze (relaxed) CCSD(T) wavefunction
produced by ORCA. The version of ORCA I currently use is 6.1. Below is an example input file
named H2CO.inp, which calculates H2CO at CCSD(T)/cc-pVTZ level using AUTOCI module.
! autoci-CCSD(T) cc-pVTZ verytightSCF"

Is it also possible to use autoci-DLPNO-CCSD(T)? Please suppose we performed a SP calculation on the DFT-optimized geometry (G16) using DLPNO-CCSD(T)-TightPNO to obtain a highly accurate energy and also a "T1 diagnostic" to ensure whether the system is really single-reference. It seems, in addition to T1 diagnostic", the orbital OCC must also be checked. Thus, the above procedure given in Multiwfn should be performed but, the SP is at DLPNO-CCSD(T)-TightPNO, not CCSD(T).

In advance, many thanks for your kind attention.
Sincerely,
Saeed

Last edited by saeed_E (2026-06-16 05:05:23)

sobereva · 2026-06-16 23:55:20

Dear Saeed,

ORCA is unable to generate wavefunction at DLPNO-CCSD(T) level, so it is not possible to perform wavefunction analysis at this level.

Best,

Tian

saeed_E · 2026-06-18 17:16:58

Thank you very much.
Saeed

saeed_E · 2026-06-18 19:55:19

Dear Tian,
For some large system, the "! autoci-CCSD(T) cc-pvtz verytightSCF" encounters problem when trying to compute "T-correction". Can we use ! autoci-CCSD cc-pvtz verytightSCF" instead with Orca 6.1.1? The main purpose is only to compute natural orbital occupancies.

Sincerely,
Saeed

sobereva · 2026-06-19 03:51:15

saeed_E wrote:

Dear Tian,
For some large system, the "! autoci-CCSD(T) cc-pvtz verytightSCF" encounters problem when trying to compute "T-correction". Can we use ! autoci-CCSD cc-pvtz verytightSCF" instead with Orca 6.1.1? The main purpose is only to compute natural orbital occupancies.
Sincerely,
Saeed

CCSD orbital occupancies are good enough, using CCSD(T) doesn't bring any evident advantage.

saeed_E · 2026-06-21 22:41:27

Thank you very much.
I sent you an email requesting an SP calculation using ORCA 6.1.1. Please note that even using CCSD, this calculation cannot be completed on my PC. Could you please run this calculation using your very powerful system?

Sincerely,
Saeed

Last edited by saeed_E (2026-06-21 22:52:39)

sobereva · 2026-06-22 04:24:39

Using autoci-CCSD even for a small system (~20 atoms) is still extremely expensive. Without strong reasons, I don't suggest performing this task.

saeed_E · 2026-06-22 07:42:29

Dear Tian,
Here is the complete report I sent for ORCA developers:
Dear ORCA Development Team,

I am reporting a reproducible issue observed in ORCA 6.1.1 during AutoCI-CCSD calculations involving relaxed density matrix evaluation.

The calculation proceeds normally through all standard electronic structure steps. The Self-Consistent Field (SCF) procedure converges without any issues. Following SCF convergence, the CCSD correlation treatment completes successfully and converges in a standard number of iterations. The coupled-cluster amplitudes converge smoothly, and the T1 diagnostic and singles norms indicate a stable wavefunction. No convergence anomalies are observed during the CCSD step.

After completion of CCSD and Lambda equation iterations, the calculation enters the density matrix evaluation phase labeled “Unrelaxed density matrices.” In this stage, the 1-particle reduced density matrix (1RDM) is successfully generated and completes normally.

Immediately after completion of the 1RDM step, the program proceeds to construct the 2-particle reduced density matrix (2RDM). At this stage, the calculation stops progressing. No error message, warning, segmentation fault, or termination is produced. The process remains active but unresponsive. CPU utilization drops to near zero and remains idle indefinitely. No further output is generated, and the calculation does not proceed beyond this point.

This behavior is fully reproducible for a medium-sized molecular system containing 15 atoms (C, N, H elements) using the cc-pVTZ basis set and TightSCF convergence criteria. The same computational setup works correctly for smaller benchmark systems (e.g., formaldehyde), where both 1RDM and 2RDM constructions complete successfully.

Input summary

! AutoCI-CCSD cc-pVTZ TightSCF

%maxcore 6000

%pal
nprocs 1
end

%autoci
density relaxed
end

xyz 0 1
[15-atom C/N/H molecular geometry as specified in the input]
System and software environment
Operating System: Ubuntu 22.04 LTS (64-bit)
CPU: Intel Core i9-9900K (8 cores / 8 threads, 3.6 GHz base frequency)
RAM: 64 GB DDR4
Swap: 2 GB (not utilized during calculation)
Storage: SSD with sufficient free space (>400 GB available)
ORCA version: 6.1.1 (x86_64 Linux build)
Parallelization: single MPI process (nprocs = 1)
OpenMPI version: 4.1.8 (bundled with ORCA distribution)
Observed behavior summary
SCF converges normally
CCSD converges normally
Lambda equations converge normally
1RDM generation completes successfully
2RDM construction does not complete
No error message or program termination is produced
CPU usage drops to near zero during the stalled phase
Process remains alive but no further progress is observed
CCSD diagnostic information
Number of amplitudes: ~12,258,429
T1 diagnostic: ~0.0103
Singles norm: stable and within expected range for convergence
Comparison system

For smaller molecular systems (e.g., formaldehyde), using the same computational settings:

AutoCI-CCSD(T)
cc-pVTZ basis
TightSCF
relaxed density enabled

the calculation completes successfully, including both 1RDM and 2RDM construction.

Request

I would appreciate clarification on the following points:

Whether this behavior in the 2RDM construction step is expected for systems of this size in AutoCI-CCSD.
Whether there are known limitations or stability issues in ORCA 6.1.1 regarding relaxed density evaluation for CCSD-level AutoCI calculations.
Whether any recommended modifications exist for reliable 2RDM generation under these conditions.

If required, I can provide the full output file, wavefunction files, or additional reduced test cases for further debugging.

Kind regards

Saeed

*****************************
Input:
! autoci-CCSD cc-pvtz verytightSCF
%maxcore 6000
%pal nprocs 2 end

%autoci density relaxed end
* xyz 0 1
H 0.20768700 -0.90797900 1.29604000
N 0.52654400 -1.41377700 0.47420400
C 1.30728600 -0.65001100 -0.26006500
H 1.88515900 -1.15220100 -1.03219800
C 1.24958900 0.74748700 -0.27522300
H 1.78539200 1.28142600 -1.04890200
C 0.27339900 1.39415300 0.46004600
H 0.00896400 1.03823400 1.44549200
H 0.12795300 2.45865600 0.32864900
C -1.45985900 -0.79156900 -0.20342700
H -1.90469700 -1.33283900 0.61917500
H -1.29711600 -1.36771000 -1.09953400
C -1.52528800 0.58976700 -0.24888000
H -1.46932500 1.08793500 -1.20535000
H -2.10589900 1.10752000 0.50279500
*
////////////////////////////////////
Output:

Program Version 6.1.1 - RELEASE -
(GIT: $487d211c$)
($2025-11-21 10:33:24 +0100$)

================================================================================
INPUT FILE
================================================================================
NAME = TS.inp
| 1> ! autoci-CCSD cc-pvtz verytightSCF
| 2> %maxcore 6000
| 3> %pal nprocs 2 end
| 4>
| 5> %autoci density relaxed end
| 6> * xyz 0 1
| 7> H 0.20768700 -0.90797900 1.29604000
| 8> N 0.52654400 -1.41377700 0.47420400
| 9> C 1.30728600 -0.65001100 -0.26006500
| 10> H 1.88515900 -1.15220100 -1.03219800
| 11> C 1.24958900 0.74748700 -0.27522300
| 12> H 1.78539200 1.28142600 -1.04890200
| 13> C 0.27339900 1.39415300 0.46004600
| 14> H 0.00896400 1.03823400 1.44549200
| 15> H 0.12795300 2.45865600 0.32864900
| 16> C -1.45985900 -0.79156900 -0.20342700
| 17> H -1.90469700 -1.33283900 0.61917500
| 18> H -1.29711600 -1.36771000 -1.09953400
| 19> C -1.52528800 0.58976700 -0.24888000
| 20> H -1.46932500 1.08793500 -1.20535000
| 21> H -2.10589900 1.10752000 0.50279500
| 22> *
| 23>
| 24>
| 25> ****END OF INPUT****
================================================================================

****************************
* Single Point Calculation *
****************************

---------------------------------
CARTESIAN COORDINATES (ANGSTROEM)
---------------------------------
H 0.207687 -0.907979 1.296040
N 0.526544 -1.413777 0.474204
C 1.307286 -0.650011 -0.260065
H 1.885159 -1.152201 -1.032198
C 1.249589 0.747487 -0.275223
H 1.785392 1.281426 -1.048902
C 0.273399 1.394153 0.460046
H 0.008964 1.038234 1.445492
H 0.127953 2.458656 0.328649
C -1.459859 -0.791569 -0.203427
H -1.904697 -1.332839 0.619175
H -1.297116 -1.367710 -1.099534
C -1.525288 0.589767 -0.248880
H -1.469325 1.087935 -1.205350
H -2.105899 1.107520 0.502795

----------------------------
CARTESIAN COORDINATES (A.U.)
----------------------------
NO LB ZA FRAG MASS X Y Z
0 H 1.0000 0 1.008 0.392472 -1.715832 2.449161
1 N 7.0000 0 14.007 0.995024 -2.671651 0.896116
2 C 6.0000 0 12.011 2.470413 -1.228343 -0.491452
3 H 1.0000 0 1.008 3.562434 -2.177344 -1.950572
4 C 6.0000 0 12.011 2.361381 1.412546 -0.520096
5 H 1.0000 0 1.008 3.373902 2.421544 -1.982138
6 C 6.0000 0 12.011 0.516649 2.634567 0.869361
7 H 1.0000 0 1.008 0.016940 1.961978 2.731584
8 H 1.0000 0 1.008 0.241796 4.646186 0.621057
9 C 6.0000 0 12.011 -2.758734 -1.495849 -0.384421
10 H 1.0000 0 1.008 -3.599356 -2.518701 1.170071
11 H 1.0000 0 1.008 -2.451194 -2.584597 -2.077818
12 C 6.0000 0 12.011 -2.882377 1.114498 -0.470315
13 H 1.0000 0 1.008 -2.776622 2.055899 -2.277781
14 H 1.0000 0 1.008 -3.979572 2.092909 0.950145

--------------------------------
INTERNAL COORDINATES (ANGSTROEM)
--------------------------------
H 0 0 0 0.000000000000 0.00000000 0.00000000
N 1 0 0 1.016324659815 0.00000000 0.00000000
C 2 1 0 1.316072770663 110.39302500 0.00000000
H 3 2 1 1.087346021245 116.32326142 166.31673059
C 3 2 1 1.398770663396 124.15164827 333.97223671
H 5 3 2 1.082014281593 118.70770431 192.20705179
C 5 3 2 1.382658429988 119.38210789 356.22901065
H 7 5 3 1.080605396388 120.24348212 40.07991911
H 7 5 3 1.082398423656 119.35906866 189.57022796
C 2 1 3 2.189091922655 79.87311622 261.31174990
H 10 2 1 1.080522146718 89.74382808 300.27287786
H 10 2 1 1.077697309721 88.18981282 184.94806052
C 10 2 1 1.383631480614 109.68433646 62.64610414
H 13 10 2 1.079878731383 119.15663616 103.65843729
H 13 10 2 1.081754412034 118.71045321 252.65682706

---------------------------
INTERNAL COORDINATES (A.U.)
---------------------------
H 0 0 0 0.000000000000 0.00000000 0.00000000
N 1 0 0 1.920575270202 0.00000000 0.00000000
C 2 1 0 2.487017108864 110.39302500 0.00000000
H 3 2 1 2.054786192963 116.32326142 166.31673059
C 3 2 1 2.643293477982 124.15164827 333.97223671
H 5 3 2 2.044710665202 118.70770431 192.20705179
C 5 3 2 2.612845769435 119.38210789 356.22901065
H 7 5 3 2.042048258010 120.24348212 40.07991911
H 7 5 3 2.045436588499 119.35906866 189.57022796
C 2 1 3 4.136784215797 79.87311622 261.31174990
H 10 2 1 2.041890938934 89.74382808 300.27287786
H 10 2 1 2.036552770636 88.18981282 184.94806052
C 10 2 1 2.614684568632 109.68433646 62.64610414
H 13 10 2 2.040675060160 119.15663616 103.65843729
H 13 10 2 2.044219582905 118.71045321 252.65682706

---------------------
BASIS SET INFORMATION
---------------------
There are 3 groups of distinct atoms

Group 1 Type H : 5s2p1d contracted to 3s2p1d pattern {311/11/1}
Group 2 Type N : 18s5p2d1f contracted to 4s3p2d1f pattern {8811/311/11/1}
Group 3 Type C : 18s5p2d1f contracted to 4s3p2d1f pattern {8811/311/11/1}

Atom 0H basis set group => 1
Atom 1N basis set group => 2
Atom 2C basis set group => 3
Atom 3H basis set group => 1
Atom 4C basis set group => 3
Atom 5H basis set group => 1
Atom 6C basis set group => 3
Atom 7H basis set group => 1
Atom 8H basis set group => 1
Atom 9C basis set group => 3
Atom 10H basis set group => 1
Atom 11H basis set group => 1
Atom 12C basis set group => 3
Atom 13H basis set group => 1
Atom 14H basis set group => 1

************************************************************
* Program running with 2 parallel MPI-processes *
* working on a common directory *
************************************************************
------------------------------------------------------------------------------
ORCA STARTUP CALCULATIONS
------------------------------------------------------------------------------
------------------------------------------------------------------------------
___
/ \ - P O W E R E D B Y -
/ \
| | | _ _ __ _____ __ __
| | | | | | | / \ | _ \ | | / |
\ \/ | | | | / \ | | | | | | / /
/ \ \ | |__| | / /\ \ | |_| | | |/ /
| | | | __ | / /__\ \ | / | \
| | | | | | | | __ | | \ | |\ \
\ / | | | | | | | | | |\ \ | | \ \
\___/ |_| |_| |__| |__| |_| \__\ |__| \__/

- O R C A' S B I G F R I E N D -
&
- I N T E G R A L F E E D E R -

v1 FN, 2020, v2 2021, v3 2022-2024
------------------------------------------------------------------------------

----------------------
SHARK INTEGRAL PACKAGE
----------------------

Number of atoms ... 15
Number of basis functions ... 342
Number of shells ... 150
Maximum angular momentum ... 3
Integral batch strategy ... SHARK/LIBINT Hybrid
RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible)
Printlevel ... 1
Contraction scheme used ... PARTIAL GENERAL contraction
Prescreening option ... SCHWARTZ
Thresh ... 1.000e-12
Tcut ... 1.000e-14
Tpresel ... 1.000e-14
Coulomb Range Separation ... NOT USED
Exchange Range Separation ... NOT USED
Multipole approximations ... NOT USED
Finite Nucleus Model ... NOT USED
CABS basis ... NOT available
Auxiliary Coulomb fitting basis ... NOT available
Auxiliary J/K fitting basis ... NOT available
Auxiliary Correlation fitting basis ... NOT available
Auxiliary 'external' fitting basis ... NOT available

Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 150
Save PGC pre-screening integrals ... done ( 0.0 sec) Dimension = 150
Calculate PGC overlap integrals ... done ( 0.0 sec) Dimension = 114
Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 114
Shell pair information
Shell pair cut-off parameter TPreSel ... 1.0e-14
Total number of shell pairs ... 11325
Shell pairs after pre-screening ... 9995
Total number of primitive shell pairs ... 16335
Primitive shell pairs kept ... 13119
la=0 lb=0: 2957 shell pairs
la=1 lb=0: 2869 shell pairs
la=1 lb=1: 653 shell pairs
la=2 lb=0: 1658 shell pairs
la=2 lb=1: 745 shell pairs
la=2 lb=2: 229 shell pairs
la=3 lb=0: 521 shell pairs
la=3 lb=1: 216 shell pairs
la=3 lb=2: 126 shell pairs
la=3 lb=3: 21 shell pairs

Checking whether 4 symmetric matrices of dimension 342 fit in memory
:Max Core in MB = 6000.00
MB in use = 13.23
MB left = 5986.77
MB needed = 1.79
Data fit in memory = YES
Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 229.664485242383 Eh

Diagonalization of the overlap matrix:
Smallest eigenvalue ... 2.191e-04
Time for diagonalization ... 0.009 sec
Threshold for overlap eigenvalues ... 1.000e-07
Number of eigenvalues below threshold ... 0
Time for construction of square roots ... 0.002 sec
Total time needed ... 0.012 sec

-------------------
DFT GRID GENERATION
-------------------

General Integration Accuracy IntAcc ... 4.388
Radial Grid Type RadialGrid ... OptM3 with GC (2021)
Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302)
Angular grid pruning method GridPruning ... 4 (adaptive)
Weight generation scheme WeightScheme... mBecke (2022)
Basis function cutoff BFCut ... 1.0000e-12
Integration weight cutoff WCut ... 1.0000e-14
Partially contracted basis set ... off
Rotationally invariant grid construction ... off
Angular grids for H and He will be reduced by one unit

Total number of grid points ... 65029
Total number of batches ... 1024
Average number of points per batch ... 63
Average number of grid points per atom ... 4335

---------------------
SHARK GRID GENERATION
---------------------

General Integration Accuracy IntAcc ... 4.388
Radial Grid Type RadialGrid ... OptM3 with GC (2021)
Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302)
Angular grid pruning method GridPruning ... 4 (adaptive)
Weight generation scheme WeightScheme... mBecke (2022)
Basis function cutoff BFCut ... 1.0000e-12
Integration weight cutoff WCut ... 1.0000e-14
Partially contracted basis set ... off
Rotationally invariant grid construction ... off
Angular grids for H and He will be reduced by one unit
Steep s-basis detected: some atoms will have their radial
grid points doubled.

Total number of grid points ... 101443
Total number of batches ... 1592
Average number of points per batch ... 63
Average number of grid points per atom ... 6763
Grids setup in 1.0 sec
Initializing property integral containers ... done ( 0.0 sec)

SHARK setup successfully completed in 1.3 seconds

Maximum memory used throughout the entire STARTUP-calculation: 42.8 MB

************************************************************
* Program running with 2 parallel MPI-processes *
* working on a common directory *
************************************************************
-------------------------------------------------------------------------------
ORCA GUESS
Start orbitals & Density for SCF / CASSCF
-------------------------------------------------------------------------------

------------
SCF SETTINGS
------------
Hamiltonian:
Ab initio Hamiltonian Method .... Hartree-Fock(GTOs)

General Settings:
Integral files IntName .... TS
Hartree-Fock type HFTyp .... RHF
Total Charge Charge .... 0
Multiplicity Mult .... 1
Number of Electrons NEL .... 46
Basis Dimension Dim .... 306
Nuclear Repulsion ENuc .... 229.6644852424 Eh

Convergence Acceleration:
AO-DIIS CNVDIIS .... on
Start iteration DIISMaxIt .... 12
Startup error DIISStart .... 0.200000
# of expansion vecs DIISMaxEq .... 5
Bias factor DIISBfac .... 1.050
Max. coefficient DIISMaxC .... 10.000
MO-DIIS CNVKDIIS .... off
Trust-Rad. Augm. Hess. CNVTRAH .... auto
Auto Start mean grad. ratio tolernc. .... 1.125000
Auto Start start iteration .... 50
Auto Start num. interpolation iter. .... 10
Max. Number of Micro iterations .... 24
Max. Number of Macro iterations .... Maxiter - #DIIS iter
Number of Davidson start vectors .... 2
Converg. threshold (grad. norm) .... 2.000e-06
Grad. Scal. Fac. for Micro threshold .... 0.100
Minimum threshold for Micro iter. .... 1.000e-02
NR start threshold (gradient norm) .... 1.000e-04
Initial trust radius .... 0.400
Minimum AH scaling param. (alpha) .... 1.000
Maximum AH scaling param. (alpha) .... 1000.000
Quad. conv. algorithm .... NR
White noise on init. David. guess .... on
Maximum white noise .... 0.010
Pseudo random numbers .... off
Inactive MOs .... canonical
Orbital update algorithm .... Taylor
Preconditioner .... Diag
Full preconditioner red. dimension .... 250
SOSCF CNVSOSCF .... on
Start iteration SOSCFMaxIt .... 150
Startup grad/error SOSCFStart .... 0.003300
Hessian update SOSCFHessUp .... L-BFGS
Autom. constraints SOSCFAutoConstrain .... off
Level Shifting CNVShift .... on
Level shift para. LevelShift .... 0.2500
Turn off err/grad. ShiftErr .... 0.0010
Zerner damping CNVZerner .... off
Static damping CNVDamp .... on
Fraction old density DampFac .... 0.7000
Max. Damping (<1) DampMax .... 0.9800
Min. Damping (>=0) DampMin .... 0.0000
Turn off err/grad. DampErr .... 0.1000

SCF Procedure:
Maximum # iterations MaxIter .... 125
SCF integral mode SCFMode .... Direct
Integral package .... SHARK and LIBINT hybrid scheme
Reset frequency DirectResetFreq .... 20
Integral Threshold Thresh .... 1.000e-12 Eh
Primitive CutOff TCut .... 1.000e-14 Eh

Convergence Tolerance:
Convergence Check Mode ConvCheckMode .... Total+1el-Energy
Convergence forced ConvForced .... 0
Energy Change TolE .... 1.000e-09 Eh
1-El. energy change .... 1.000e-06 Eh
Orbital Gradient TolG .... 2.000e-06
Orbital Rotation angle TolX .... 2.000e-06
DIIS Error TolErr .... 1.000e-08

------------------------------
INITIAL GUESS: MODEL POTENTIAL
------------------------------
Loading Hartree-Fock densities ... done
Calculating cut-offs ... done
Initializing the effective Hamiltonian ... done
Setting up the integral package (SHARK) ... done
Starting the Coulomb interaction ... done ( 0.1 sec)
Making the grid ... done ( 0.1 sec)
Mapping shells ... done
Starting the XC term evaluation ... done ( 0.1 sec)
Transforming the Hamiltonian ... done ( 0.0 sec)
Diagonalizing the Hamiltonian ... done ( 0.0 sec)
Back transforming the eigenvectors ... done ( 0.0 sec)
Now organizing SCF variables ... done
------------------
INITIAL GUESS DONE ( 0.3 sec)
------------------
**** ENERGY FILE WAS UPDATED (TS.en.tmp) ****
Finished Guess after 0.4 sec
Maximum memory used throughout the entire GUESS-calculation: 23.0 MB

************************************************************
* Program running with 2 parallel MPI-processes *
* working on a common directory *
************************************************************

-------------------------------------------------------------------------------------------
ORCA LEAN-SCF
memory conserving SCF solver
-------------------------------------------------------------------------------------------

----------------------------------------D-I-I-S--------------------------------------------
Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec)
-------------------------------------------------------------------------------------------
*** Starting incremental Fock matrix formation ***
1 -248.6486219115701886 0.00e+00 1.35e-03 3.54e-02 2.53e-01 0.700 10.9
2 -248.7570213303691560 -1.08e-01 1.11e-03 2.93e-02 1.56e-01 0.700 9.9
***Turning on AO-DIIS***
3 -248.8229855655734184 -6.60e-02 6.16e-04 1.52e-02 9.96e-02 0.700 11.3
4 -248.8650921346115581 -4.21e-02 1.37e-03 3.61e-02 7.06e-02 0.000 11.1
5 -248.9592095554006903 -9.41e-02 1.73e-04 4.55e-03 5.46e-03 0.000 11.1
*** Initializing SOSCF ***
---------------------------------------S-O-S-C-F--------------------------------------
Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec)
--------------------------------------------------------------------------------------
6 -248.9595551390129060 -3.46e-04 1.15e-04 3.36e-03 2.93e-03 10.1
*** Restarting incremental Fock matrix formation ***
7 -248.9596487018749542 -9.36e-05 7.38e-05 1.76e-03 1.08e-03 10.9
8 -248.9596846348235601 -3.59e-05 9.75e-05 2.11e-03 7.07e-04 9.1
9 -248.9597029313588621 -1.83e-05 2.30e-05 6.34e-04 1.15e-04 9.1
10 -248.9597046694169933 -1.74e-06 1.84e-05 4.47e-04 1.17e-04 8.3
11 -248.9597052095345191 -5.40e-07 2.54e-06 4.68e-05 3.31e-05 8.2
12 -248.9597052503118277 -4.08e-08 1.10e-06 2.70e-05 1.51e-05 7.5
13 -248.9597052587562587 -8.44e-09 3.77e-07 8.32e-06 2.96e-06 7.1
14 -248.9597052596621154 -9.06e-10 1.04e-07 2.06e-06 1.00e-06 6.6
**** Energy Check signals convergence ****

*****************************************************
* SUCCESS *
* SCF CONVERGED AFTER 14 CYCLES *
*****************************************************

**** ENERGY FILE WAS UPDATED (TS.en.tmp) ****

----------------
TOTAL SCF ENERGY
----------------

Total Energy : -248.95970525973283 Eh -6774.53799 eV

Components:
Nuclear Repulsion : 229.66448524238277 Eh 6249.48836 eV
Electronic Energy : -478.62419050211560 Eh -13024.02635 eV
One Electron Energy: -790.87809535754729 Eh -21520.88708 eV
Two Electron Energy: 312.25390485543170 Eh 8496.86072 eV

Virial components:
Potential Energy : -497.66775460409889 Eh -13542.22808 eV
Kinetic Energy : 248.70804934436606 Eh 6767.69009 eV
Virial Ratio : 2.00101185271659

---------------
SCF CONVERGENCE
---------------

Last Energy change ... 9.0586e-10 Tolerance : 1.0000e-09
Last MAX-Density change ... 2.0571e-06 Tolerance : 1.0000e-08
Last RMS-Density change ... 1.0391e-07 Tolerance : 1.0000e-09
Last DIIS Error ... 2.9309e-03 Tolerance : 1.0000e-08
Last Orbital Gradient ... 1.0045e-06 Tolerance : 2.0000e-06
Last Orbital Rotation ... 1.4286e-06 Tolerance : 2.0000e-06

----------------
ORBITAL ENERGIES
----------------

NO OCC E(Eh) E(eV)
0 2.0000 -15.547049 -423.0567
1 2.0000 -11.261424 -306.4389
2 2.0000 -11.254184 -306.2419
3 2.0000 -11.249026 -306.1016
4 2.0000 -11.230133 -305.5875
5 2.0000 -11.216618 -305.2197
6 2.0000 -1.198207 -32.6049
7 2.0000 -1.051297 -28.6073
8 2.0000 -1.024480 -27.8775
9 2.0000 -0.885755 -24.1026
10 2.0000 -0.810586 -22.0572
11 2.0000 -0.741222 -20.1697
12 2.0000 -0.678779 -18.4705
13 2.0000 -0.653189 -17.7742
14 2.0000 -0.619023 -16.8445
15 2.0000 -0.581466 -15.8225
16 2.0000 -0.551885 -15.0176
17 2.0000 -0.540631 -14.7113
18 2.0000 -0.510630 -13.8949
19 2.0000 -0.501189 -13.6380
20 2.0000 -0.422415 -11.4945
21 2.0000 -0.353737 -9.6257
22 2.0000 -0.302216 -8.2237
23 0.0000 0.090270 2.4564
24 0.0000 0.140409 3.8207
25 0.0000 0.143800 3.9130
26 0.0000 0.156744 4.2652
27 0.0000 0.177905 4.8410
28 0.0000 0.194409 5.2901
29 0.0000 0.197475 5.3736
30 0.0000 0.208272 5.6674
31 0.0000 0.224624 6.1123
32 0.0000 0.240937 6.5562
33 0.0000 0.256679 6.9846
*Only the first 10 virtual orbitals were printed.

********************************
* MULLIKEN POPULATION ANALYSIS *
********************************

-----------------------
MULLIKEN ATOMIC CHARGES
-----------------------
0 H : 0.148507
1 N : -0.337967
2 C : -0.059003
3 H : 0.152279
4 C : -0.187530
5 H : 0.164504
6 C : -0.232739
7 H : 0.139539
8 H : 0.152014
9 C : -0.236819
10 H : 0.158702
11 H : 0.168514
12 C : -0.324793
13 H : 0.149021
14 H : 0.145769
Sum of atomic charges: 0.0000000

--------------------------------
MULLIKEN REDUCED ORBITAL CHARGES
--------------------------------
0 H s : 0.785559 s : 0.785559
pz : 0.018209 p : 0.061385
px : 0.020562
py : 0.022615
dz2 : 0.001032 d : 0.004548
dxz : 0.000914
dyz : 0.001513
dx2y2 : 0.000655
dxy : 0.000434

1 N s : 3.570598 s : 3.570598
pz : 1.070911 p : 3.712000
px : 1.075012
py : 1.566077
dz2 : 0.007668 d : 0.052408
dxz : 0.007039
dyz : 0.015632
dx2y2 : 0.009447
dxy : 0.012622
f0 : 0.000235 f : 0.002960
f+1 : 0.000402
f-1 : 0.000517
f+2 : 0.000371
f-2 : 0.000766
f+3 : 0.000255
f-3 : 0.000413

2 C s : 3.246379 s : 3.246379
pz : 0.940766 p : 2.660284
px : 0.848510
py : 0.871009
dz2 : 0.023306 d : 0.139657
dxz : 0.016874
dyz : 0.039383
dx2y2 : 0.026969
dxy : 0.033125
f0 : 0.001088 f : 0.012683
f+1 : 0.001408
f-1 : 0.001581
f+2 : 0.002458
f-2 : 0.001751
f+3 : 0.002357
f-3 : 0.002040

3 H s : 0.823392 s : 0.823392
pz : 0.007178 p : 0.021993
px : 0.006563
py : 0.008252
dz2 : 0.000595 d : 0.002336
dxz : 0.000465
dyz : 0.000484
dx2y2 : 0.000434
dxy : 0.000357

4 C s : 3.211802 s : 3.211802
pz : 1.021474 p : 2.881515
px : 0.966872
py : 0.893169
dz2 : 0.012928 d : 0.084685
dxz : 0.012735
dyz : 0.023377
dx2y2 : 0.018010
dxy : 0.017635
f0 : 0.000747 f : 0.009527
f+1 : 0.001250
f-1 : 0.001054
f+2 : 0.001774
f-2 : 0.001312
f+3 : 0.001738
f-3 : 0.001653

5 H s : 0.808110 s : 0.808110
pz : 0.009030 p : 0.025058
px : 0.008697
py : 0.007331
dz2 : 0.000664 d : 0.002328
dxz : 0.000437
dyz : 0.000436
dx2y2 : 0.000480
dxy : 0.000312

6 C s : 3.290471 s : 3.290471
pz : 0.967747 p : 2.833472
px : 0.856236
py : 1.009488
dz2 : 0.030703 d : 0.102332
dxz : 0.014453
dyz : 0.010975
dx2y2 : 0.032022
dxy : 0.014178
f0 : 0.000626 f : 0.006464
f+1 : 0.001027
f-1 : 0.001068
f+2 : 0.000892
f-2 : 0.000874
f+3 : 0.000820
f-3 : 0.001157

7 H s : 0.828504 s : 0.828504
pz : 0.010530 p : 0.029592
px : 0.010209
py : 0.008852
dz2 : 0.000682 d : 0.002365
dxz : 0.000779
dyz : 0.000649
dx2y2 : 0.000182
dxy : 0.000073

8 H s : 0.820020 s : 0.820020
pz : 0.007346 p : 0.025850
px : 0.007768
py : 0.010736
dz2 : 0.000214 d : 0.002116
dxz : 0.000033
dyz : 0.000646
dx2y2 : 0.000560
dxy : 0.000663

9 C s : 3.290661 s : 3.290661
pz : 1.049039 p : 2.836277
px : 0.858355
py : 0.928884
dz2 : 0.014267 d : 0.103367
dxz : 0.008633
dyz : 0.039368
dx2y2 : 0.014974
dxy : 0.026124
f0 : 0.000525 f : 0.006513
f+1 : 0.000408
f-1 : 0.001538
f+2 : 0.000990
f-2 : 0.000427
f+3 : 0.001702
f-3 : 0.000924

10 H s : 0.812981 s : 0.812981
pz : 0.009457 p : 0.026188
px : 0.008733
py : 0.007997
dz2 : 0.000562 d : 0.002129
dxz : 0.000409
dyz : 0.000503
dx2y2 : 0.000371
dxy : 0.000284

11 H s : 0.803054 s : 0.803054
pz : 0.009157 p : 0.026234
px : 0.008796
py : 0.008282
dz2 : 0.000730 d : 0.002198
dxz : 0.000375
dyz : 0.000564
dx2y2 : 0.000285
dxy : 0.000243

12 C s : 3.267271 s : 3.267271
pz : 1.036816 p : 2.959717
px : 0.996985
py : 0.925915
dz2 : 0.014376 d : 0.091704
dxz : 0.009622
dyz : 0.034258
dx2y2 : 0.012280
dxy : 0.021169
f0 : 0.000667 f : 0.006102
f+1 : 0.000365
f-1 : 0.001387
f+2 : 0.000893
f-2 : 0.000390
f+3 : 0.001408
f-3 : 0.000992

13 H s : 0.821942 s : 0.821942
pz : 0.008898 p : 0.026724
px : 0.009922
py : 0.007905
dz2 : 0.000740 d : 0.002313
dxz : 0.000550
dyz : 0.000585
dx2y2 : 0.000248
dxy : 0.000190

14 H s : 0.824468 s : 0.824468
pz : 0.008580 p : 0.027471
px : 0.011123
py : 0.007768
dz2 : 0.000530 d : 0.002292
dxz : 0.000425
dyz : 0.000468
dx2y2 : 0.000573
dxy : 0.000296

*******************************
* LOEWDIN POPULATION ANALYSIS *
*******************************

----------------------
LOEWDIN ATOMIC CHARGES
----------------------
0 H : -0.135627
1 N : 0.238651
2 C : -0.120243
3 H : -0.034162
4 C : -0.045669
5 H : -0.036170
6 C : 0.146483
7 H : -0.034790
8 H : -0.028751
9 C : 0.138417
10 H : -0.037364
11 H : -0.039126
12 C : 0.071690
13 H : -0.042821
14 H : -0.040518

-------------------------------
LOEWDIN REDUCED ORBITAL CHARGES
-------------------------------
0 H s : 0.785992 s : 0.785992
pz : 0.100533 p : 0.289095
px : 0.074675
py : 0.113886
dz2 : 0.017163 d : 0.060541
dxz : 0.013244
dyz : 0.017142
dx2y2 : 0.007910
dxy : 0.005082

1 N s : 3.037431 s : 3.037431
pz : 1.083269 p : 3.554787
px : 1.019297
py : 1.452222
dz2 : 0.032683 d : 0.156624
dxz : 0.030188
dyz : 0.038176
dx2y2 : 0.028805
dxy : 0.026772
f0 : 0.001090 f : 0.012507
f+1 : 0.001321
f-1 : 0.002401
f+2 : 0.002093
f-2 : 0.002171
f+3 : 0.001682
f-3 : 0.001748

2 C s : 2.720746 s : 2.720746
pz : 0.895887 p : 2.763315
px : 0.848609
py : 1.018819
dz2 : 0.085245 d : 0.568882
dxz : 0.068625
dyz : 0.149165
dx2y2 : 0.122780
dxy : 0.143066
f0 : 0.006996 f : 0.067300
f+1 : 0.007509
f-1 : 0.007939
f+2 : 0.012123
f-2 : 0.008066
f+3 : 0.015713
f-3 : 0.008953

3 H s : 0.860470 s : 0.860470
pz : 0.060228 p : 0.147081
px : 0.045472
py : 0.041381
dz2 : 0.006690 d : 0.026612
dxz : 0.006002
dyz : 0.005769
dx2y2 : 0.004024
dxy : 0.004127

4 C s : 2.706453 s : 2.706453
pz : 0.954530 p : 2.891107
px : 0.935122
py : 1.001454
dz2 : 0.057093 d : 0.405668
dxz : 0.051821
dyz : 0.099740
dx2y2 : 0.095702
dxy : 0.101312
f0 : 0.004254 f : 0.042442
f+1 : 0.004798
f-1 : 0.004861
f+2 : 0.007094
f-2 : 0.004302
f+3 : 0.010526
f-3 : 0.006607

5 H s : 0.845685 s : 0.845685
pz : 0.066608 p : 0.162403
px : 0.050798
py : 0.044996
dz2 : 0.007694 d : 0.028082
dxz : 0.005749
dyz : 0.005997
dx2y2 : 0.004333
dxy : 0.004309

6 C s : 2.709795 s : 2.709795
pz : 0.951395 p : 2.750694
px : 0.834975
py : 0.964324
dz2 : 0.103662 d : 0.360769
dxz : 0.059597
dyz : 0.043416
dx2y2 : 0.098284
dxy : 0.055810
f0 : 0.002540 f : 0.032259
f+1 : 0.004904
f-1 : 0.004863
f+2 : 0.005105
f-2 : 0.004945
f+3 : 0.004576
f-3 : 0.005327

7 H s : 0.841740 s : 0.841740
pz : 0.072980 p : 0.164678
px : 0.045349
py : 0.046349
dz2 : 0.009583 d : 0.028371
dxz : 0.007720
dyz : 0.007967
dx2y2 : 0.002119
dxy : 0.000983

8 H s : 0.847015 s : 0.847015
pz : 0.038574 p : 0.154574
px : 0.037001
py : 0.078999
dz2 : 0.002879 d : 0.027163
dxz : 0.000213
dyz : 0.008636
dx2y2 : 0.007890
dxy : 0.007545

9 C s : 2.728441 s : 2.728441
pz : 0.977040 p : 2.764494
px : 0.761501
py : 1.025953
dz2 : 0.045704 d : 0.339259
dxz : 0.021070
dyz : 0.132764
dx2y2 : 0.061175
dxy : 0.078546
f0 : 0.003770 f : 0.029389
f+1 : 0.001838
f-1 : 0.005145
f+2 : 0.005449
f-2 : 0.001984
f+3 : 0.006888
f-3 : 0.004315

10 H s : 0.850093 s : 0.850093
pz : 0.063420 p : 0.159718
px : 0.049477
py : 0.046821
dz2 : 0.007563 d : 0.027553
dxz : 0.005766
dyz : 0.006835
dx2y2 : 0.003784
dxy : 0.003605

11 H s : 0.848830 s : 0.848830
pz : 0.070297 p : 0.162487
px : 0.043654
py : 0.048536
dz2 : 0.008911 d : 0.027809
dxz : 0.005463
dyz : 0.008216
dx2y2 : 0.002859
dxy : 0.002361

12 C s : 2.710584 s : 2.710584
pz : 0.977196 p : 2.858047
px : 0.871762
py : 1.009088
dz2 : 0.049485 d : 0.330111
dxz : 0.027163
dyz : 0.122394
dx2y2 : 0.059334
dxy : 0.071734
f0 : 0.004175 f : 0.029568
f+1 : 0.001430
f-1 : 0.005208
f+2 : 0.005444
f-2 : 0.002701
f+3 : 0.005719
f-3 : 0.004890

13 H s : 0.847827 s : 0.847827
pz : 0.073145 p : 0.166299
px : 0.047416
py : 0.045738
dz2 : 0.009499 d : 0.028695
dxz : 0.007073
dyz : 0.008126
dx2y2 : 0.002179
dxy : 0.001818

14 H s : 0.845839 s : 0.845839
pz : 0.058693 p : 0.165972
px : 0.060794
py : 0.046485
dz2 : 0.007179 d : 0.028707
dxz : 0.006119
dyz : 0.005804
dx2y2 : 0.005321
dxy : 0.004285

*****************************
* MAYER POPULATION ANALYSIS *
*****************************

NA - Mulliken gross atomic population
ZA - Total nuclear charge
QA - Mulliken gross atomic charge
VA - Mayer's total valence
BVA - Mayer's bonded valence
FA - Mayer's free valence

ATOM NA ZA QA VA BVA FA
0 H 0.8515 1.0000 0.1485 1.0135 1.0135 0.0000
1 N 7.3380 7.0000 -0.3380 2.9927 2.9927 -0.0000
2 C 6.0590 6.0000 -0.0590 3.9619 3.9619 0.0000
3 H 0.8477 1.0000 0.1523 0.9769 0.9769 0.0000
4 C 6.1875 6.0000 -0.1875 3.6500 3.6500 0.0000
5 H 0.8355 1.0000 0.1645 0.9733 0.9733 0.0000
6 C 6.2327 6.0000 -0.2327 3.8897 3.8897 -0.0000
7 H 0.8605 1.0000 0.1395 0.9729 0.9729 -0.0000
8 H 0.8480 1.0000 0.1520 0.9730 0.9730 -0.0000
9 C 6.2368 6.0000 -0.2368 3.8328 3.8328 0.0000
10 H 0.8413 1.0000 0.1587 0.9751 0.9751 0.0000
11 H 0.8315 1.0000 0.1685 0.9724 0.9724 0.0000
12 C 6.3248 6.0000 -0.3248 3.7996 3.7996 0.0000
13 H 0.8510 1.0000 0.1490 0.9780 0.9780 0.0000
14 H 0.8542 1.0000 0.1458 0.9747 0.9747 0.0000

Mayer bond orders larger than 0.100000
B( 0-H , 1-N ) : 0.9824 B( 1-N , 2-C ) : 1.6160 B( 1-N , 9-C ) : 0.3250
B( 2-C , 3-H ) : 0.9840 B( 2-C , 4-C ) : 1.2712 B( 4-C , 5-H ) : 0.9611
B( 4-C , 6-C ) : 1.4153 B( 6-C , 7-H ) : 0.9636 B( 6-C , 8-H ) : 0.9731
B( 6-C , 12-C ) : 0.4171 B( 9-C , 10-H ) : 0.9718 B( 9-C , 11-H ) : 0.9700
B( 9-C , 12-C ) : 1.4374 B( 12-C , 13-H ) : 0.9674 B( 12-C , 14-H ) : 0.9674

-------
TIMINGS
-------

Total SCF time: 0 days 0 hours 2 min 17 sec

Total time .... 137.348 sec
Sum of individual times .... 131.395 sec ( 95.7%)

SCF preparation .... 0.072 sec ( 0.1%)
Fock matrix formation .... 130.974 sec ( 95.4%)
Startup .... 0.004 sec ( 0.0% of F)
Coulomb+Exchange Fock .... 136.884 sec (104.5% of F)
Diagonalization .... 0.000 sec ( 0.0%)
Density matrix formation .... 0.039 sec ( 0.0%)
Total Energy calculation .... 0.015 sec ( 0.0%)
Population analysis .... 0.016 sec ( 0.0%)
Orbital Transformation .... 0.031 sec ( 0.0%)
Orbital Orthonormalization .... 0.000 sec ( 0.0%)
DIIS solution .... 0.142 sec ( 0.1%)
SOSCF solution .... 0.104 sec ( 0.1%)
Finished LeanSCF after 137.4 sec

Maximum memory used throughout the entire LEANSCF-calculation: 27.4 MB

--------------------------------------------------------------------------------
ORCA-MATRIX DRIVEN AUTOCI
--------------------------------------------------------------------------------

---------------------------- Technical Information -----------------------------
Print Level ... 4
Maximum memory ... 6000 MB
Keep MO Integrals ... 0
Use MO Integrals from disk ... 0
Number of parallel MPI processes ... 2
MO Integrals transformation type ... 0 (Full Canonical)
Use general autoci evaluation module ... 0

------------------------------ Wavefunction Type -------------------------------
Correlation treatment ... CCSD
Frozen core treatment type ... 1
Reference Wavefunction: ... RHF
Internal orbitals: 6 ... 22
Virtual orbitals: 23 ... 305

---------------------------- Converger Information -----------------------------
Maximum number of iterations ... 50
Maximum depth of DIIS extrapolation ... 5
Convergence tolerance (max. residuum) ... 1.000e-06
Level shift for amplitude update ... 2.000e-01
Denominator for amplitude update ... Orbital Energies
Number of multiplicity blocks ... 1
... BLOCK 0: Mult = 1 Roots = 1
... Number of states to solve ... 1

---------------------------------- Properties ----------------------------------
1-body density matrix ... true
2-body density matrix ... true
Memory used before INT TRAFO: 2 MB
--------------- Full MO transformation and Fock matrix formation ---------------
Initializing the integral package ... done

--------------------------
CLOSED-SHELL FOCK OPERATOR
--------------------------

Recanonicalizing the internal orbitals
Recanonicalizing the virtual orbitals
Storing new orbitals
Formation of (pq|rs) ...
-------------------------
SHARK FULL TRANSFORMATION (Coulomb order)
-------------------------

Orbital Range Operator 0: 0- 305 to 0- 305 NBasis= 306

Preparing matrix containers ...
Transformed integrals for op=0,0 ... TS.MO14_op0.tmp
Now calling half transformation ...

-------------------------
SHARK HALF TRANSFORMATION
-------------------------

Number of basis functions ... 306
Number of operators ... 1
Operator 0: 0- 305

Integral generator used ... SHARK
Contraction scheme used ... GENERAL CONTRACTION
MaxCore in resort ... 6000 MB

Half transformed integrals for op= 0 ... TS.SHARK_MNPQ0.tmp
Resorted half transformed integrals ... TS.SHARK_PQMN0.tmp
Starting integral generation + half trafo...
Half trafo (general) done. Total time = 86.0 sec. integrals= 35.3 sec trafo= 50.0 sec
Starting integral resorting ... done (191.9 sec)

SHARK half integral transformation done. Total time =278.0 sec.

Completing integral transformation ... done (166.2 sec)

SHARK Full integral transformation done. Total time =446.6 sec.

ok ( 446.560 sec)
Sorting MO integrals ... ok ( 370.933 sec)

------------------------------- Entering solver --------------------------------
-----------------------
MP2 GUESS
-----------------------
Initial guess performed in 2.406 sec
E(0) ... -248.959705260 Eh
E(MP2) ... -1.079589028 Eh
E(TOT) ... -250.039294288 Eh
<T|T> ... 0.373124011

----------------------------- RHF CCSD Iterations ------------------------------
Number of amplitudes to optimize: 12258429

It. E(ECORR) Delta-E MaxResidual Time
1 -1.079589028 6.88338e-15 1.41731e-02 74.48
*** Turning on DIIS ***
2 -1.072508750 7.08028e-03 5.66082e-03 60.16
3 -1.099987224 -2.74785e-02 2.23710e-03 60.24
4 -1.105997592 -6.01037e-03 1.30624e-03 58.97
5 -1.107688847 -1.69125e-03 8.71179e-04 59.06
6 -1.108163337 -4.74490e-04 4.64592e-04 58.08
7 -1.108271375 -1.08038e-04 2.72311e-04 59.79
8 -1.108323988 -5.26133e-05 1.20846e-04 59.43
9 -1.108327366 -3.37733e-06 5.33287e-05 58.83
10 -1.108332865 -5.49896e-06 2.85703e-05 58.04
11 -1.108332330 5.34670e-07 1.81490e-05 58.77
12 -1.108333557 -1.22746e-06 1.12068e-05 59.96
13 -1.108334012 -4.54603e-07 6.37516e-06 59.10
14 -1.108334376 -3.63949e-07 2.82195e-06 59.31
15 -1.108334508 -1.31922e-07 1.05171e-06 61.81
16 -1.108334519 -1.10813e-08 4.08177e-07 57.26

-------------------- Calculation CONVERGED in 16 iterations --------------------

------------------------------- RHF CCSD Energy --------------------------------
E(0) ... -248.959705260
E(CORR) ... -1.108334519
E(TOT) ... -250.068039779
Singles Norm <S|S>**1/2 ... 0.076981958
T1 diagnostic ... 0.013202297

------------------ Largest amplitudes (non-orthogonal basis) -------------------
0 IJAB( 0): 22 -> 23 22 -> 23 : 0.059458123
1 IJAB( 0): 21 -> 23 21 -> 23 : 0.055241204
2 IJAB( 0): 22 -> 25 22 -> 25 : 0.036623947
3 IJAB( 0): 22 -> 23 22 -> 25 : 0.031121968
4 IJAB( 0): 22 -> 25 22 -> 23 : 0.031121968
5 IA(11): 21 -> 23 0 -> 0 : 0.024985793
6 IJAB( 0): 21 -> 24 21 -> 23 : 0.024249254
7 IJAB( 0): 21 -> 23 21 -> 24 : 0.024249254
8 IA(11): 22 -> 23 0 -> 0 : 0.024004505
9 IJAB( 0): 21 -> 24 21 -> 24 : 0.023359489
10 IJAB( 0): 22 -> 23 21 -> 23 : 0.022823285
11 IJAB( 0): 18 -> 23 18 -> 23 : 0.021853298
12 IJAB( 0): 22 -> 24 21 -> 23 : 0.018281053
13 IJAB( 0): 22 -> 23 21 -> 25 : 0.017375050
14 IJAB( 0): 21 -> 34 18 -> 23 : 0.017317575
15 IA(11): 22 -> 25 0 -> 0 : 0.017011073
16 IJAB( 0): 22 -> 34 18 -> 23 : 0.016161518
17 IJAB( 0): 22 -> 24 21 -> 25 : 0.015708261
18 IJAB( 0): 22 -> 25 22 -> 27 : 0.015548404
19 IJAB( 0): 22 -> 27 22 -> 25 : 0.015548404

-------------------------- RHF CCSD Lambda Iterations --------------------------

Pre-computing constant intermediates ... done ( 87.2 sec)

It. MaxResidual Time
1 4.52834e-03 184.31
*** Turning on DIIS ***
2 8.18451e-04 84.85
3 5.48249e-04 83.25
4 2.39184e-04 65.14
5 1.90956e-04 65.03
6 8.88677e-05 65.37
7 4.94908e-05 65.50
8 1.87923e-05 66.81
9 1.04927e-05 66.03
10 5.68730e-06 64.85
11 3.75083e-06 64.96
12 1.84981e-06 65.67
13 9.87749e-07 65.49

-------------------- Calculation CONVERGED in 13 iterations --------------------
Singles Norm <S|S>**1/2 ... 0.060222641
T1 diagnostic ... 0.010328098

------------------ Largest amplitudes (non-orthogonal basis) -------------------
0 IJAB( 0): 22 -> 23 22 -> 23 : 0.053751129
1 IJAB( 0): 21 -> 23 21 -> 23 : 0.050002136
2 IJAB( 0): 22 -> 25 22 -> 25 : 0.033943213
3 IJAB( 0): 22 -> 23 22 -> 25 : 0.028972619
4 IJAB( 0): 22 -> 25 22 -> 23 : 0.028972619
5 IJAB( 0): 21 -> 24 21 -> 23 : 0.022702104
6 IJAB( 0): 21 -> 23 21 -> 24 : 0.022702104
7 IJAB( 0): 21 -> 24 21 -> 24 : 0.021954885
8 IJAB( 0): 22 -> 23 21 -> 23 : 0.021774613
9 IJAB( 0): 18 -> 23 18 -> 23 : 0.019770580
10 IA(11): 22 -> 23 0 -> 0 : 0.017953011
11 IA(11): 21 -> 23 0 -> 0 : 0.017708765
12 IJAB( 0): 22 -> 24 21 -> 23 : 0.016827906
13 IJAB( 0): 21 -> 34 18 -> 23 : 0.016209657
14 IJAB( 0): 22 -> 23 21 -> 25 : 0.016107263
15 IJAB( 0): 22 -> 34 18 -> 23 : 0.015127390
16 IJAB( 0): 22 -> 24 21 -> 25 : 0.014878994
17 IA(11): 22 -> 25 0 -> 0 : 0.014448021
18 IJAB( 0): 22 -> 27 22 -> 25 : 0.014412737
19 IJAB( 0): 22 -> 25 22 -> 27 : 0.014412737

----------------------------------------------
Unrelaxed density matrices
----------------------------------------------
1RDM ... done ( 1.3 sec)

2RDM ...

saeed_E · 2026-06-22 12:27:56

Dear Tian,
Do you have any suggestions in place of the AUTO-CI CCSD (relaxed density) for large systems? I need accurate natural orbital occupancies (NOO) calculations. If so, what should be the content of the "orca.jsaon.conf" text file?

Sincerely,
Saeed

Last edited by saeed_E (2026-06-22 12:29:54)

sobereva · 2026-06-22 22:42:19

The easiest way of obtaining something like NOO is performing finite-temperature DFT calculation in ORCA, the cost is nearly the same as common DFT.

Also you can use the MDCI code in ORCA to obtain CCSD unrelaxed density (or density corresponding to CCD with orbital optimization) to yield NOO, the efficiency is much higher than the AUTOCI-CCSD while the accuracy is not much poorer than the CCSD relaxed density. Alternatively, using Gaussian to yield CCSD relaxed density, it is not quite expensive for your system.

By the way, I don't know what is your purpose of obtaining NOO, in most cases you can use an inexpensive basis set for this purpose, e.g. using def-TZVP instead of cc-pVTZ, is usually enough.

saeed_E · Yesterday 16:06:59

NOO means natural orbital occupancies.
You so kindly mentioned:
Also you can use the MDCI code in ORCA to obtain CCSD unrelaxed density (or density corresponding to CCD with orbital optimization) to yield NOO, the efficiency is much higher than the AUTOCI-CCSD while the accuracy is not much poorer than the CCSD relaxed density. Alternatively, using Gaussian to yield CCSD relaxed density, it is not quite expensive for your system.

Could you please let me know what should be the ORCA input file for my system exactly? In addition, the orca.jason.conf should be created. Please also let me know what should be its contents to be used in Multiwfn (1000--->98).

Sincerely,
Saeed

Multiwfn forum

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#10 2026-06-22 22:42:19

Re: Wave function analysis at DLPNO-CCSD(T)

#11 Yesterday 16:06:59

Re: Wave function analysis at DLPNO-CCSD(T)

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