Example 7.11 This example shows two jobs which request variants of time-dependent density functional theory calculations. The first job, using the default value of RPA = FALSE, performs TDDFT in the Tamm-Dancoff approximation (TDA). The second job, with RPA = TRUE performs a both TDA and full TDDFT calculations.
$comment methyl peroxy radical TDDFT/TDA and full TDDFT with 6-31+G* $end $molecule 0 2 C 1.00412 -0.18045 0.00000 O -0.24600 0.59615 0.00000 O -1.31237 -0.23026 0.00000 H 1.81077 0.56720 0.00000 H 1.03665 -0.80545 -0.90480 H 1.03665 -0.80545 0.90480 $end $rem EXCHANGE b CORRELATION lyp CIS_N_ROOTS 5 BASIS 6-31+G* SCF_CONVERGENCE 7 $end @@@ $molecule read $end $rem EXCHANGE b CORRELATION lyp CIS_N_ROOTS 5 CIS_MAX_CYCLES 40 RPA true BASIS 6-31+G* SCF_CONVERGENCE 7 $end
Example 7.12 This example shows a calculation of the excited states of a formamide-water complex within a reduced excitation space of the orbitals located on formamide.
$comment formamide-water TDDFT/TDA in reduced excitation space $end $molecule 0 1 H 1.13 0.49 -0.75 C 0.31 0.50 -0.03 N -0.28 -0.71 0.08 H -1.09 -0.75 0.67 H 0.23 -1.62 -0.22 O -0.21 1.51 0.47 O -2.69 1.94 -0.59 H -2.59 2.08 -1.53 H -1.83 1.63 -0.30 $end $rem EXCHANGE b3lyp CIS_N_ROOTS 10 BASIS 6-31++G** TRNSS TRUE TRTYPE 1 CUTOCC 60 CUTVIR 40 CISTR_PRINT TRUE N_SOL 6 $end $solute 1 2 3 4 5 6 $end
Example 7.13 SF-TDDFT SP calculation of the 6 lowest states of the TMM diradical using recommended 50-50 functional.
$molecule 0 3 C C 1 CC1 C 1 CC2 2 A2 C 1 CC2 2 A2 3 180.0 H 2 C2H 1 C2CH 3 0.0 H 2 C2H 1 C2CH 4 0.0 H 3 C3Hu 1 C3CHu 2 0.0 H 3 C3Hd 1 C3CHd 4 0.0 H 4 C3Hu 1 C3CHu 2 0.0 H 4 C3Hd 1 C3CHd 3 0.0 CC1 = 1.35 CC2 = 1.47 C2H = 1.083 C3Hu = 1.08 C3Hd = 1.08 C2CH = 121.2 C3CHu = 120.3 C3CHd = 121.3 A2 = 121.0 $end $rem EXCHANGE gen BASIS 6-31G* SCF_GUESS core SCF_CONVERGENCE 10 MAX_SCF_CYCLES 100 SPIN_FLIP 1 CIS_N_ROOTS 6 CIS_CONVERGENCE 10 MAX_CIS_CYCLES 100 $end $xc_functional X HF 0.50 X S 0.08 X B 0.42 C VWN 0.19 C LYP 0.81 $end
Example 7.14 SF-DFT with non-collinear exchange-correlation functional for low-lying states of .
$comment Non-collinear SF-DFT calculation for CH2 at 3B1 state geometry from EOM-CCSD(fT) calculation $end $molecule 0 3 C H 1 rCH H 1 rCH 2 HCH rCH = 1.0775 HCH = 133.29 $end $rem EXCHANGE PBE0 BASIS cc-pVTZ SPIN_FLIP 1 WANG_ZIEGLER_KERNEL TRUE SCF_CONVERGENCE 10 CIS_N_ROOTS 6 CIS_CONVERGENCE 10 $end
Example 7.15 SF-DFT calculation with collinear B5050LYP for para-benzyne with wave-function analaysis (natural orbitals and NTOs) performed by libwfa.
$comment Para-benzyne diradical Equilibrium singlet state geom from: J. Chem. Phys. 136, 204103 (2012) Enu = 187.2138176166 hartree $end $molecule 0 3 H 2.145810 -1.225292 0.000000 C 1.201382 -0.709285 0.000000 C 1.201382 0.709285 0.000000 H 2.145810 1.225292 0.000000 C 0.000000 1.335664 0.000000 C -1.201382 0.709285 0.000000 H -2.145810 1.225291 0.000000 C -1.201382 -0.709285 0.000000 H -2.145810 -1.225291 0.000000 C 0.000000 -1.335664 0.000000 $end $rem METHOD = b5050lyp BASIS = 6-31G* CIS_N_ROOTS = 4 SPIN_FLIP = true NEW_DFT = true STATE_ANALYSIS = true WFA_REF_STATE = 1 MOLDEN_FORMAT = true NTO_PAIRS = 4 $end