Multiwfn forum

Alexey

Member

Registered: 2024-06-28

Posts: 16

T1 state optimization problem

Hello, I am trying to calculate the phosphorescence spectrum of a transition metal (copper) complex. I have attached the XYZ file. I am having a problem with DFT in Orca not being able to match the experimental phosphorescence result (2.83 eV). I have tried various functionals and found that using TDA improves the result for all the functionals I have tried, without it the triplet is greatly underestimated. However I am still not getting close to the experiment, my best result is 2.3 eV using wB97x/def2TZVP with TDA. LC-PBE and LC-BLYP give results around 2-2.2 eV, as do r2scan50, MN15, b3lyp and pbe0. Interestingly, using pbeh-3c I was getting 2.45 eV in the middle of an optimization run, but then the optimization broke down and I got a negative number. If anyone knows, please tell me which DFT functionals are recommended in my case, or should I still use multi-reference methods, thanks.

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Cu 3.037023693 13.146441031 7.179215576
Cl 2.212517022 13.019565014 9.142739063
N 5.460505320 12.215472452 5.858057461
C 4.737813670 13.266919410 6.374465924
C 6.321793735 12.628308171 4.691855075
C 5.769806524 14.041468444 4.399304099
H 4.992384247 13.969811470 3.637328253
H 6.547421698 14.702735698 4.013817322
C 5.144976460 14.576079369 5.711217531
C 5.468031558 10.908300345 6.460193046
C 4.617158948 9.899965177 5.950828140
C 4.700314596 8.619200478 6.498765456
H 4.062138915 7.834819899 6.111859326
C 5.562131871 8.335214456 7.543670857
H 5.612756559 7.333139974 7.951822090
C 6.329109545 9.350242271 8.090153125
H 6.963209501 9.135023879 8.940720335
C 6.291429342 10.647734208 7.579745018
C 3.541889813 10.161505989 4.901721403
H 3.665117221 11.182473857 4.543599997
C 2.139646699 10.073868259 5.532174714
H 1.375245341 10.340955997 4.798348488
H 2.038426430 10.746566669 6.387285155
H 1.925676393 9.063385710 5.887593601
C 3.629097583 9.216767480 3.692682877
H 2.888402809 9.499055392 2.940581317
H 3.423514393 8.183054949 3.977798414
H 4.613035344 9.241438264 3.224101412
C 7.075666328 11.731049238 8.307280086
H 7.004023797 12.642358911 7.718998138
C 6.436914793 12.031905565 9.675286157
H 6.965220982 12.853351984 10.166149650
H 6.487981125 11.162557910 10.335085023
H 5.388588870 12.314051430 9.573834151
C 8.564625221 11.391161645 8.472085618
H 9.095447695 12.235174493 8.918856911
H 9.038791300 11.161479673 7.516681647
H 8.711107838 10.531929634 9.129756889
C 7.807353260 12.668661660 5.087242647
H 8.399786629 12.985542850 4.226109491
H 8.158375251 11.680282837 5.385368482
H 7.999922454 13.365150822 5.900903575
C 6.181231371 11.708480008 3.478098247
H 6.812851681 12.083522038 2.669929108
H 5.157336365 11.672620418 3.111120844
H 6.508416472 10.693754923 3.709117546
C 6.121169192 15.435427346 6.586107383
H 6.745723347 14.827638161 7.238726685
H 6.781368334 15.994282402 5.916081298
C 5.235637191 16.423881416 7.366265085
H 4.948816748 16.014410514 8.340261232
H 5.741514080 17.372868101 7.556254179
C 4.023288814 16.568846517 6.481537348
C 3.028266020 17.541177656 6.527953644
H 3.071761694 18.340464892 7.260169357
C 1.985403609 17.470556834 5.612908683
C 0.790972524 18.383643380 5.463097500
H 1.042834317 19.440923481 5.567261566
H 0.046854311 18.157352766 6.235616496
C 0.250683086 18.031995096 4.058342216
H 0.721769551 18.683107793 3.317818266
H -0.828096278 18.166260177 3.973064416
C 0.695845046 16.572642559 3.809607998
H -0.075423527 15.867616782 4.141658332
H 0.882216514 16.362581992 2.754305356
C 1.930513042 16.437031148 4.670824732
C 2.916640631 15.458776086 4.633254054
H 2.868087510 14.658422866 3.902751587
C 3.971711581 15.537324683 5.541719301