dalton磷光速率计算结果精确度问题

shaowenhao28

各位老师好，我用dalton分别计算了同一个小分子（C,O,H,Br）的磷光速率和Tn-S0之间的SOCME，发现有些三重态虽然到基态的SOCME小，磷光速率却很大。

这是Tn-S0 SOCME的计算结果， 删去了一些不相干的信息：
@ Excited state no:    1 in symmetry 1  ( A  )
----------------------------------------------

@ Excitation energy :  0.10245254     au
@                       2.7878753     eV;   22485.732     cm-1;   268.98909     kJ / mol

@ Total energy :       -3540.8493     au

@ Operator type:    X1MNF-SO
@ Spin-orbit coupling constant (X1MNF-SO) :   4.3502780     cm-1
                                            1.98213254E-05 au

@ Operator type:    Y1MNF-SO
@ Spin-orbit coupling constant (Y1MNF-SO) :  -3.2970288     cm-1
                                           -1.50223686E-05 au

@ Operator type:    Z1MNF-SO
@ Spin-orbit coupling constant (Z1MNF-SO) :  -1.6351422     cm-1
                                           -7.45025631E-06 au



@ Excited state no:    2 in symmetry 1  ( A  )
----------------------------------------------

@ Excitation energy :  0.11357370     au
@                       3.0904977     eV;   24926.546     cm-1;   298.18771     kJ / mol

@ Total energy :       -3540.8382     au

@ Operator type:    X1MNF-SO
@ Spin-orbit coupling constant (X1MNF-SO) :   22.893866     cm-1
                                            1.04312128E-04 au

@ Operator type:    Y1MNF-SO
@ Spin-orbit coupling constant (Y1MNF-SO) :  -6.2197125     cm-1
                                           -2.83390955E-05 au

@ Operator type:    Z1MNF-SO
@ Spin-orbit coupling constant (Z1MNF-SO) :  -4.8346676     cm-1
                                           -2.20283666E-05 au



@ Excited state no:    3 in symmetry 1  ( A  )
----------------------------------------------

@ Excitation energy :  0.12952635     au
@                       3.5245912     eV;   28427.747     cm-1;   340.07137     kJ / mol

@ Total energy :       -3540.8223     au

@ Operator type:    X1MNF-SO
@ Spin-orbit coupling constant (X1MNF-SO) :   1.9424815     cm-1
                                            8.85059717E-06 au

@ Operator type:    Y1MNF-SO
@ Spin-orbit coupling constant (Y1MNF-SO) :   1.1904373     cm-1
                                            5.42403134E-06 au

@ Operator type:    Z1MNF-SO
@ Spin-orbit coupling constant (Z1MNF-SO) :  0.24867407     cm-1
                                            1.13304243E-06 au


可以看到就SOCME来说T2-S0 > T1-S0 > T3-S0，但是磷光速率的计算结果却显示kp的趋势是T3 > T2 > T1

Phosphorescence transition rate from excited state no.  1
(Triplet->singlet transition, high-temperature limit)


Transition energy:  2.788 eV
    or   444.726 nm

  Length gauge / mean field spin-orbit integrals:
Partial rates (AMFI): X-polarization  17.210     Transition moment :  8.644E-04
  Length gauge / mean field spin-orbit integrals:
Partial rates (AMFI): Y-polarization  5.5756     Transition moment :  4.920E-04
  Length gauge / mean field spin-orbit integrals:
Partial rates (AMFI): Z-polarization  8.5183     Transition moment :  6.081E-04

  Phosphorescence - length gauge / mean field spin-orbit integrals:
Oscillator strength (/2PI)     (AMFI)    1.477296E-08
Dipole strength [a.u.]         (AMFI)    1.358989E-06
Dipole strength E-40 [esu**2 cm**2]      8.779712E-02
Total transition rate          (AMFI)    1.043476E+01 s-1
Total phosphorescence lifetime (AMFI)    9.583356E-02 s

Phosphorescence transition rate from excited state no.  2
(Triplet->singlet transition, high-temperature limit)


Transition energy:  3.090 eV
    or   401.179 nm

  Length gauge / mean field spin-orbit integrals:
Partial rates (AMFI): X-polarization  306.11     Transition moment :  3.123E-03
  Length gauge / mean field spin-orbit integrals:
Partial rates (AMFI): Y-polarization  681.53     Transition moment :  4.660E-03
  Length gauge / mean field spin-orbit integrals:
Partial rates (AMFI): Z-polarization  11.616     Transition moment :  6.084E-04

  Phosphorescence - length gauge / mean field spin-orbit integrals:
Oscillator strength (/2PI)     (AMFI)    3.837365E-07
Dipole strength [a.u.]         (AMFI)    3.184391E-05
Dipole strength E-40 [esu**2 cm**2]      2.057268E+00
Total transition rate          (AMFI)    3.330874E+02 s-1
Total phosphorescence lifetime (AMFI)    3.002215E-03 s

Phosphorescence transition rate from excited state no.  3
(Triplet->singlet transition, high-temperature limit)


Transition energy:  3.525 eV
    or   351.769 nm

  Length gauge / mean field spin-orbit integrals:
Partial rates (AMFI): X-polarization  478.39     Transition moment :  3.206E-03
  Length gauge / mean field spin-orbit integrals:
Partial rates (AMFI): Y-polarization  3457.9     Transition moment :  8.619E-03
  Length gauge / mean field spin-orbit integrals:
Partial rates (AMFI): Z-polarization  93.818     Transition moment :  1.420E-03

  Phosphorescence - length gauge / mean field spin-orbit integrals:
Oscillator strength (/2PI)     (AMFI)    1.189904E-06
Dipole strength [a.u.]         (AMFI)    8.658146E-05
Dipole strength E-40 [esu**2 cm**2]      5.593573E+00
Total transition rate          (AMFI)    1.343376E+03 s-1
Total phosphorescence lifetime (AMFI)    7.443931E-04 s



请问计算结果可信吗？ 除了SOCME和能量差，是否还有别的因素会导致磷光速率反常？

另外附上输入文件
Tn-S0的SOCME:
**DALTON INPUT
.RUN RESPONS
**INTEGRALS
.MNF-SO
**WAVE FUNCTIONS
.DFT
B3LYP
**RESPONS
.TRPFLG
*LINEAR
.SINGLE RESIDUE
.PROPRT
X1MNF-SO
.PROPRT
Y1MNF-SO
.PROPRT
Z1MNF-SO  
.PRINT
3
.ROOTS
5
**END OF DALTON INPUT


磷光速率：
**DALTON INPUT
.RUN RESPONS
**INTEGRALS
.MNF-SO
**WAVE FUNCTIONS
.DFT
B3LYP
**RESPONS
*QUADRATIC
.MNFPHO
.PRINT
3  
.ROOTS
5
**END OF DALTON INPUT

abin

basis set?

ggdh

完全不顾kasha规则的么。。

shaowenhao28

abin 发表于 2019-8-27 09:13
basis set?

basis set 是cc-pVDZ

shaowenhao28

ggdh 发表于 2019-8-27 19:38
完全不顾kasha规则的么。。

kasha's rule应该只是在实验中体现吧，计算的时候算得是理论上如果从Tn发射时的磷光速率，不考虑internal convertion

abin

shaowenhao28 发表于 2019-8-28 08:50
basis set 是cc-pVDZ

.MNF-SO
Calculates the atomic mean-field spin-orbit integrals as described in Ref. [138]. As the calculation of these integrals require a proper description of the atomic states, reliable results can only be expected for generally contracted basis sets such as the ANO sets, and in some cases also the correlation-consistent basis sets ((aug-)cc-p(C)VXZ)).

手册如此说的。 不清楚， in some cases， 是否包含你的情形。

桀桀桀桀桀桀

说来T2和T3的磷光发射速率不用乘上Boltzmann因子再和T1的比较吗？