xiongyan21
commented
1 year ago Test cc-multref and eom-ccsd-ro-c2n have illustrated these, but whether they are that useful are not that sure.
During the calculation of the excitation energies of benzenenitrile with cr-eomccsd(t) using 6-311+G**, left-hand RHF CCSD eliminates large T1. T1 DIAGNOSTIC = 0.01242250 NORM OF THE T1 VECTOR= 0.07657741 NORM OF THE T2 VECTOR= 0.59922187
THE FIVE LARGEST T1 AMPLITUDES ARE: T1 AMPLITUDE IS 0.021751 FOR I= 26 -> A= 83 T1 AMPLITUDE IS -0.016913 FOR I= 27 -> A= 29 T1 AMPLITUDE IS 0.015660 FOR I= 27 -> A= 85 T1 AMPLITUDE IS 0.011694 FOR I= 26 -> A= 40 T1 AMPLITUDE IS 0.011573 FOR I= 27 -> A= 89
SYMMETRY OF THE GROUND STATE LEFT EIGENSTATE: A
THE LARGEST LA1 AND LA2 AMPLITUDES FOR THIS ROOT ARE
LA2= -0.0630523240 FOR I,J -> A,B = 18 18 24 24
LA2= -0.0629133442 FOR I,J -> A,B = 19 19 21 21
Aug-cc-pvdz gives no large T1 T1 DIAGNOSTIC = 0.01146088 NORM OF THE T1 VECTOR= 0.07064960 NORM OF THE T2 VECTOR= 0.60319056
THE FIVE LARGEST T1 AMPLITUDES ARE: T1 AMPLITUDE IS -0.016615 FOR I= 27 -> A= 33 T1 AMPLITUDE IS -0.013666 FOR I= 20 -> A= 83 T1 AMPLITUDE IS 0.013355 FOR I= 26 -> A= 122 T1 AMPLITUDE IS -0.011377 FOR I= 26 -> A= 127 T1 AMPLITUDE IS -0.010380 FOR I= 27 -> A= 120
For pyrimidine, left-hand CCSD only slightly reduce it LAMBDA VECTOR ITERATIONS HAVE CONVERGED, THE LARGEST LA1 AND LA2 AMPLITUDES ARE LA1= -0.0281285132 FOR IA -> AA = 19 22 LA1= 0.0297835618 FOR IA -> AA = 21 23 LA1= -0.0281285132 FOR IB -> AB = 19 22 LA1= 0.0297835618 FOR IB -> AB = 21 23 LA2= -0.0452797187 FOR IA,JA -> AA, BA = 19 21 22 23 LA2= -0.0452797187 FOR IB,JB -> AB, BB = 19 21 22 23 LA2= -0.0264579256 FOR IA,JB -> AA, BB = 17 17 22 22 LA2= -0.0257401068 FOR IA,JB -> AA, BB = 17 17 28 28 LA2= 0.0372744944 FOR IA,JB -> AA, BB = 17 19 22 28 LA2= 0.0272761121 FOR IA,JB -> AA, BB = 17 19 28 22 LA2= -0.0342615704 FOR IA,JB -> AA, BB = 17 21 23 28 LA2= 0.0272761121 FOR IA,JB -> AA, BB = 19 17 22 28 LA2= 0.0372744944 FOR IA,JB -> AA, BB = 19 17 28 22 LA2= -0.0773651427 FOR IA,JB -> AA, BB = 19 19 22 22 LA2= -0.0258829794 FOR IA,JB -> AA, BB = 19 19 23 23 LA2= 0.0491933301 FOR IA,JB -> AA, BB = 19 21 23 22 LA2= -0.0342615704 FOR IA,JB -> AA, BB = 21 17 28 23 LA2= 0.0491933301 FOR IA,JB -> AA, BB = 21 19 22 23 LA2= -0.0354905272 FOR IA,JB -> AA, BB = 21 21 22 22 LA2= -0.0786330542 FOR IA,JB -> AA, BB = 21 21 23 23
T2 are not increased.
For guanine, T1= 0.0425056105 FOR IA -> AA = 32 40 T1= -0.0268004283 FOR IA -> AA = 32 43 T1= 0.0265046414 FOR IA -> AA = 33 41 T1= -0.0312247009 FOR IA -> AA = 39 40 T1= 0.0425056105 FOR IB -> AB = 32 40 T1= -0.0268004283 FOR IB -> AB = 32 43 T1= 0.0265046414 FOR IB -> AB = 33 41 T1= -0.0312247009 FOR IB -> AB = 39 40 T2= -0.0297079404 FOR IA,JB -> AA, BB = 32 32 40 40 T2= -0.0251091842 FOR IA,JB -> AA, BB = 36 36 40 40 T2= -0.0462035596 FOR IA,JB -> AA, BB = 36 36 43 43 T2= -0.0427053335 FOR IA,JB -> AA, BB = 38 38 41 41 T2= -0.0592687422 FOR IA,JB -> AA, BB = 39 39 40 40 T2= -0.0280336372 FOR IA,JB -> AA, BB = 39 39 43 43 LA1= 0.0259158043 FOR IA -> AA = 32 40 LA1= 0.0259158043 FOR IB -> AB = 32 40 LA2= -0.0267334606 FOR IA,JB -> AA, BB = 32 32 40 40 LA2= -0.0429905863 FOR IA,JB -> AA, BB = 36 36 43 43 LA2= -0.0388607469 FOR IA,JB -> AA, BB = 38 38 41 41 LA2= -0.0534364758 FOR IA,JB -> AA, BB = 39 39 40 40 LA2= -0.0254383683 FOR IA,JB -> AA, BB = 39 39 43 43
Very Best Regards!
In test cc-ip-ohmius, the T1 and T2 diagnostics during CCSD iterations are THE LARGEST T1 AND T2 AMPLITUDES ARE T1= 0.2018973459 FOR IA -> AA = 5 6 T1= 0.0397724873 FOR IA -> AA = 5 10 T1= 0.2018973459 FOR IB -> AB = 5 6 T1= 0.0397724873 FOR IB -> AB = 5 10 T2= 0.0279971297 FOR IA,JA -> AA, BA = 3 4 8 9 T2= 0.0279971297 FOR IB,JB -> AB, BB = 3 4 8 9 T2= -0.0338303476 FOR IA,JB -> AA, BB = 2 2 6 6 T2= -0.0250007710 FOR IA,JB -> AA, BB = 2 3 11 9 T2= -0.0250007710 FOR IA,JB -> AA, BB = 2 4 11 8 T2= -0.0250007710 FOR IA,JB -> AA, BB = 3 2 9 11 T2= -0.0531259253 FOR IA,JB -> AA, BB = 3 3 6 6 T2= -0.0544393902 FOR IA,JB -> AA, BB = 3 3 9 9 T2= -0.0385098292 FOR IA,JB -> AA, BB = 3 4 9 8 T2= 0.0286939477 FOR IA,JB -> AA, BB = 3 5 9 6 T2= -0.0250007710 FOR IA,JB -> AA, BB = 4 2 8 11 T2= -0.0385098292 FOR IA,JB -> AA, BB = 4 3 8 9 T2= -0.0531259253 FOR IA,JB -> AA, BB = 4 4 6 6 T2= -0.0544393902 FOR IA,JB -> AA, BB = 4 4 8 8 T2= 0.0286939477 FOR IA,JB -> AA, BB = 4 5 8 6 T2= 0.0286939477 FOR IA,JB -> AA, BB = 5 3 6 9 T2= 0.0286939477 FOR IA,JB -> AA, BB = 5 4 6 8 T2= -0.3449575187 FOR IA,JB -> AA, BB = 5 5 6 6 T2= 0.0588078333 FOR IA,JB -> AA, BB = 5 5 6 7 T2= 0.0588078333 FOR IA,JB -> AA, BB = 5 5 7 6 T2= -0.0286997530 FOR IA,JB -> AA, BB = 5 5 7 7
In the calculation of IP of pyrimidine(B3LYP 6-311+G** optimized), the diagnostics are THE LARGEST T1 AND T2 AMPLITUDES ARE T1= -0.0359705125 FOR IA -> AA = 19 22 T1= -0.0350638905 FOR IA -> AA = 21 23 T1= -0.0359705125 FOR IB -> AB = 19 22 T1= -0.0350638905 FOR IB -> AB = 21 23 T2= 0.0488768010 FOR IA,JA -> AA, BA = 19 21 22 23 T2= 0.0488768010 FOR IB,JB -> AB, BB = 19 21 22 23 T2= -0.0287244011 FOR IA,JB -> AA, BB = 17 17 22 22 T2= -0.0261849474 FOR IA,JB -> AA, BB = 17 17 23 23 T2= -0.0258396211 FOR IA,JB -> AA, BB = 17 17 28 28 T2= -0.0391172835 FOR IA,JB -> AA, BB = 17 19 22 28 T2= -0.0291050702 FOR IA,JB -> AA, BB = 17 19 28 22 T2= -0.0358559910 FOR IA,JB -> AA, BB = 17 21 23 28 T2= -0.0291050702 FOR IA,JB -> AA, BB = 19 17 22 28 T2= -0.0391172835 FOR IA,JB -> AA, BB = 19 17 28 22 T2= -0.0824694061 FOR IA,JB -> AA, BB = 19 19 22 22 T2= -0.0288211420 FOR IA,JB -> AA, BB = 19 19 23 23 T2= -0.0253826796 FOR IA,JB -> AA, BB = 19 19 28 28 T2= -0.0521552989 FOR IA,JB -> AA, BB = 19 21 23 22 T2= -0.0358559910 FOR IA,JB -> AA, BB = 21 17 28 23 T2= -0.0521552989 FOR IA,JB -> AA, BB = 21 19 22 23 T2= -0.0402216543 FOR IA,JB -> AA, BB = 21 21 22 22 T2= -0.0833999432 FOR IA,JB -> AA, BB = 21 21 23 23
and the result is perhaps somewhat high(6-311G**) ---- SUMMARY OF IP-EOMCCSDt CALCULATIONS ---- SPIN IONIZATION TOTAL SYMM MULT ENERGY (H) ENERGY (H) ITERATIONS A 2 0.3725033044 -263.2853948485 CONVERGED
But even with these, the results can be OK, e.g. for benzene(no T1), pyridazine(no T1), quinoline(no T1, eomccsd), guanine(with both, eomccsd), etc.
Pyrazine has no large T1, but the result is ～|2.2|% deviating 9.63, using eomccsdt
For test cc-ip-n3, there are THE LARGEST T1 AND T2 AMPLITUDES ARE T1= 0.0312076768 FOR IA -> AA = 7 22 T1= 0.0312076768 FOR IA -> AA = 8 23 T1= 0.0312076768 FOR IB -> AB = 7 22 T1= 0.0312076768 FOR IB -> AB = 8 23 T2= -0.0382404404 FOR IA,JA -> AA, BA = 10 11 22 23 T2= -0.0382404404 FOR IB,JB -> AB, BB = 10 11 22 23 T2= -0.0457569476 FOR IA,JB -> AA, BB = 7 7 22 22 T2= -0.0296841259 FOR IA,JB -> AA, BB = 7 8 22 23 T2= -0.0296841259 FOR IA,JB -> AA, BB = 8 7 23 22 T2= -0.0457569476 FOR IA,JB -> AA, BB = 8 8 23 23 T2= 0.0391129878 FOR IA,JB -> AA, BB = 10 10 19 22 T2= 0.0391129878 FOR IA,JB -> AA, BB = 10 10 22 19 T2= -0.0788315555 FOR IA,JB -> AA, BB = 10 10 22 22 T2= 0.0263823115 FOR IA,JB -> AA, BB = 10 11 19 23 T2= 0.0263823115 FOR IA,JB -> AA, BB = 10 11 22 20 T2= -0.0536377408 FOR IA,JB -> AA, BB = 10 11 22 23 T2= 0.0263823115 FOR IA,JB -> AA, BB = 11 10 20 22 T2= 0.0263823115 FOR IA,JB -> AA, BB = 11 10 23 19 T2= -0.0536377408 FOR IA,JB -> AA, BB = 11 10 23 22 T2= 0.0391129878 FOR IA,JB -> AA, BB = 11 11 20 23 T2= 0.0391129878 FOR IA,JB -> AA, BB = 11 11 23 20 T2= -0.0788315555 FOR IA,JB -> AA, BB = 11 11 23 23
Are the diagnostics still useful ?
Actually, there is printed one in RHF excitation energy calculation, e.g., for phenylacetylene
T1 DIAGNOSTIC = 0.01190666 NORM OF THE T1 VECTOR= 0.07339758 NORM OF THE T2 VECTOR= 0.58993522
THE FIVE LARGEST T1 AMPLITUDES ARE: T1 AMPLITUDE IS -0.025121 FOR I= 26 -> A= 82 T1 AMPLITUDE IS -0.020746 FOR I= 27 -> A= 85 T1 AMPLITUDE IS -0.019252 FOR I= 24 -> A= 81 T1 AMPLITUDE IS 0.016240 FOR I= 21 -> A= 80 T1 AMPLITUDE IS -0.014613 FOR I= 25 -> A= 95
For RHF eomccsd excitation calculation of primidine, T1 becomes T1 DIAGNOSTIC = 0.01166332 NORM OF THE T1 VECTOR= 0.06997992 NORM OF THE T2 VECTOR= 0.56335593
THE FIVE LARGEST T1 AMPLITUDES ARE: T1 AMPLITUDE IS -0.020395 FOR I= 25 -> A= 79 T1 AMPLITUDE IS -0.019243 FOR I= 24 -> A= 78 T1 AMPLITUDE IS 0.014375 FOR I= 23 -> A= 34 T1 AMPLITUDE IS -0.013392 FOR I= 24 -> A= 31 T1 AMPLITUDE IS 0.010937 FOR I= 23 -> A= 48
and it seems T1 doesn't very much depend on basis sets.
Very Best Regards!