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标题: 改变自旋多重度如何快速计算单点能 [打印本页]

作者
Author: nanokey 时间: 前天 23:42
标题: 改变自旋多重度如何快速计算单点能
各位老师好，最近我计算过渡态能量遇到一点问题，我用 m06-2x def2-tzvp优化了中性结构，用m06-2x ma-def2-qzvp计算了单点能，现在我想用中性的结构直接计算阴离子状态的单点能，但是花费时间太长一直算不出来，请问有什么方法可以快速计算吗？（不改变基组和泛函的情况下）

中性结构优化 opt freq m06-2x def2-tzvp 电荷和自旋（0，1）
中性结构计算单点能 m06-2x ma-def2-qzvp  电荷和自旋（0，1）
离子结构计算单点能 m06-2x ma-def2-qzvp  电荷和自旋（-1，2）
跑着一直是DIIS: error= 1.30D-04 at cycle xx NSaved=  17

作者
Author: 北大-陶豫 时间: yesterday 00:01
本帖最后由北大-陶豫于 2026-2-20 00:03 编辑

读中性结构的波函数作为初猜吧，类似如下的输入文件：

%oldchk=neutral.chk
%chk=anion.chk
# M062X def2qzvp Guess=Read

复制代码

作者
Author: wal 时间: yesterday 00:01
用更多的核运行任务即可快速计算

作者
Author: nanokey 时间: yesterday 00:36

北大-陶豫发表于 2026-2-20 00:01
读中性结构的波函数作为初猜吧，类似如下的输入文件：

我试试，感谢老师！

作者
Author: nanokey 时间: yesterday 00:37

wal 发表于 2026-2-20 00:01
用更多的核运行任务即可快速计算

超算设置最多32，已经跑三天了。。。

作者
Author: sobereva 时间: yesterday 07:49
上传用了#P的输出文件便于别人准确判断情况

作者
Author: nanokey 时间: yesterday 13:09

sobereva 发表于 2026-2-20 07:49
上传用了#P的输出文件便于别人准确判断情况

sober老师好，其实就是类似计算垂直电子亲合能的过程，用中性结构计算阴离子状态的电子能量，总共25个原子，可能是ma-def2-QZVP太耗时了，就是一直跑着没有得到能量

Cycle  36  Pass 1  IDiag  1:
RMSU=  3.37D-05 CP:  1.09D+00  1.18D+00 -1.33D+00 -2.68D-01 -2.77D+00
                  CP:  3.00D+00 -3.00D+00  3.00D+00  1.26D+00 -1.94D+00
                  CP: -3.00D+00  3.00D+00  1.09D+00  3.00D+00  1.74D+00
E= -1953.40647374155    Delta-E=    -0.000006942614 Rises=F Damp=F
DIIS: error= 1.30D-04 at cycle  36 NSaved=  18.
NSaved=18 IEnMin= 3 EnMin= -1953.40693610640    IErMin=18 ErrMin= 1.30D-04
ErrMax= 1.30D-04  0.00D+00 EMaxC= 1.00D-01 BMatC= 1.26D-04 BMatP= 9.69D-05
IDIUse=3 WtCom= 9.99D-01 WtEn= 1.40D-03
Large coefficients: NSaved= 18 BigCof= 18.77 CofMax= 10.00 Det=-4.61D-10
Inversion failed.  Reducing to 17 matrices.
Large coefficients: NSaved= 17 BigCof= 18.94 CofMax= 10.00 Det=-4.61D-10
Inversion failed.  Reducing to 16 matrices.
Large coefficients: NSaved= 16 BigCof= 17.34 CofMax= 10.00 Det=-4.64D-10
Inversion failed.  Reducing to 15 matrices.
Large coefficients: NSaved= 15 BigCof= 14.03 CofMax= 10.00 Det=-4.65D-10
Inversion failed.  Reducing to 14 matrices.
Large coefficients: NSaved= 14 BigCof= 10.08 CofMax= 10.00 Det=-4.72D-10
Inversion failed.  Reducing to 13 matrices.
Large coefficients: NSaved= 13 BigCof= 16.26 CofMax= 10.00 Det=-4.74D-10
Inversion failed.  Reducing to 12 matrices.
Large coefficients: NSaved= 12 BigCof= 10.53 CofMax= 10.00 Det=-4.95D-10
Inversion failed.  Reducing to 11 matrices.
Coeff-Com:  0.127D+01 0.269D+01-0.344D+01 0.432D+00 0.758D+01-0.884D+01
Coeff-Com:  0.881D+00 0.497D+01-0.875D+01 0.131D+01 0.290D+01
Coeff-En: 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.000D+00
Coeff-En: 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.100D+01
Coeff:    0.127D+01 0.268D+01-0.344D+01 0.431D+00 0.757D+01-0.883D+01
Coeff:    0.880D+00 0.496D+01-0.874D+01 0.131D+01 0.289D+01
Gap=    0.042 Goal= None Shift= 0.000
Gap=    0.793 Goal= None Shift= 0.000
RMSDP=5.36D-03 MaxDP=3.14D+00 DE=-6.94D-06 OVMax= 4.44D-02

Cycle  37  Pass 1  IDiag  1:
RMSU=  7.95D-04 CP:  1.08D+00  1.09D+00 -1.24D+00 -3.08D-02 -8.89D-01
                  CP:  3.00D+00 -3.00D+00  1.11D+00  2.28D+00 -2.35D+00
                  CP: -3.00D+00  1.84D+00  3.38D-01  3.00D+00  3.00D+00
                  CP:  3.33D-01
E= -1953.40640655767    Delta-E=       0.000067183884 Rises=F Damp=F
DIIS: error= 1.37D-04 at cycle  37 NSaved=  12.
NSaved=12 IEnMin= 3 EnMin= -1953.40693610640    IErMin=11 ErrMin= 1.30D-04
ErrMax= 1.37D-04  0.00D+00 EMaxC= 1.00D-01 BMatC= 9.72D-05 BMatP= 1.15D-04
IDIUse=3 WtCom= 9.99D-01 WtEn= 1.37D-03
Large coefficients: NSaved= 12 BigCof= 13.67 CofMax= 10.00 Det=-4.95D-10
Inversion failed.  Reducing to 11 matrices.
Large coefficients: NSaved= 11 BigCof= 13.79 CofMax= 10.00 Det=-2.80D-09
Inversion failed.  Reducing to 10 matrices.
Large coefficients: NSaved= 10 BigCof= 13.30 CofMax= 10.00 Det=-2.80D-09
Inversion failed.  Reducing to  9 matrices.
Large coefficients: NSaved=  9 BigCof= 10.36 CofMax= 10.00 Det=-2.92D-09
Inversion failed.  Reducing to  8 matrices.
Rare condition: small coef for last iteration:  0.000D+00
Coeff-Com: -0.150D+00-0.402D+00 0.170D+00 0.499D+01-0.311D+01-0.246D+01
Coeff-Com:  0.230D+00 0.173D+01
Coeff-En: 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.000D+00
Coeff-En: 0.000D+00 0.100D+01
Coeff:    -0.150D+00-0.402D+00 0.170D+00 0.499D+01-0.311D+01-0.246D+01
Coeff:    0.230D+00 0.173D+01
Gap=    0.042 Goal= None Shift= 0.000
Gap=    0.329 Goal= None Shift= 0.000
RMSDP=7.70D-03 MaxDP=5.57D+00 DE= 6.72D-05 OVMax= 6.00D-02

Cycle  38  Pass 1  IDiag  1:
RMSU=  1.05D-03 CP:  1.08D+00  1.38D+00 -2.54D+00 -9.89D-01 -2.65D+00
                  CP:  3.00D+00 -3.00D+00  3.00D+00  3.00D+00 -3.00D+00
                  CP: -3.00D+00  3.00D+00  1.15D+00  3.00D+00  3.00D+00
                  CP:  3.00D+00  1.18D+00
E= -1953.40651322436    Delta-E=    -0.000106666690 Rises=F Damp=F
DIIS: error= 1.34D-04 at cycle  38 NSaved= 9.
NSaved= 9 IEnMin= 2 EnMin= -1953.40693610640    IErMin= 7 ErrMin= 1.30D-04
ErrMax= 1.34D-04  0.00D+00 EMaxC= 1.00D-01 BMatC= 9.09D-05 BMatP= 9.72D-05
IDIUse=3 WtCom= 9.99D-01 WtEn= 1.34D-03
Large coefficients: NSaved=  9 BigCof= 17.27 CofMax= 10.00 Det=-3.31D-09
Inversion failed.  Reducing to  8 matrices.
Large coefficients: NSaved=  8 BigCof= 17.58 CofMax= 10.00 Det=-3.32D-09
Inversion failed.  Reducing to  7 matrices.
Coeff-Com:  0.190D+00-0.122D+01 0.274D+00 0.133D+01-0.171D+01 0.124D+01
Coeff-Com:  0.890D+00
Coeff-En: 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.000D+00
Coeff-En: 0.100D+01
Coeff:    0.190D+00-0.122D+01 0.273D+00 0.133D+01-0.171D+01 0.124D+01
Coeff:    0.890D+00
Gap=    0.042 Goal= None Shift= 0.000
Gap=    0.329 Goal= None Shift= 0.000
RMSDP=8.69D-03 MaxDP=7.81D+00 DE=-1.07D-04 OVMax= 4.71D-02

Cycle  39  Pass 1  IDiag  1:
RMSU=  2.48D-03 CP:  1.09D+00  1.78D+00 -1.74D+00 -1.53D+00 -2.80D+00
                  CP:  3.00D+00 -3.00D+00  3.00D+00  3.00D+00 -3.00D+00
                  CP: -3.00D+00  3.00D+00  1.75D+00  3.00D+00  3.00D+00
                  CP:  3.00D+00  1.52D+00  2.70D+00
E= -1953.40637428046    Delta-E=       0.000138943899 Rises=F Damp=F
DIIS: error= 1.31D-04 at cycle  39 NSaved= 8.
NSaved= 8 IEnMin= 2 EnMin= -1953.40693610640    IErMin= 8 ErrMin= 1.31D-04
ErrMax= 1.31D-04  0.00D+00 EMaxC= 1.00D-01 BMatC= 1.01D-04 BMatP= 9.09D-05
IDIUse=3 WtCom= 9.99D-01 WtEn= 1.34D-03
Rare condition: small coef for last iteration:  0.000D+00
Coeff-Com:  0.391D+00-0.167D+01 0.314D+00 0.290D+01-0.316D+01 0.130D+01
Coeff-Com:  0.142D+01-0.496D+00
Coeff-En: 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.000D+00
Coeff-En: 0.000D+00 0.100D+01
Coeff:    0.391D+00-0.167D+01 0.314D+00 0.290D+01-0.316D+01 0.130D+01
Coeff:    0.142D+01-0.496D+00
Gap=    0.042 Goal= None Shift= 0.000
Gap=    0.329 Goal= None Shift= 0.000
RMSDP=2.42D-03 MaxDP=1.22D+00 DE= 1.39D-04 OVMax= 1.81D-02

Cycle  40  Pass 1  IDiag  1:
RMSU=  6.04D-04 CP:  1.10D+00  1.71D+00 -1.20D+00 -1.41D+00 -2.68D+00
                  CP:  3.00D+00 -3.00D+00  3.00D+00  3.00D+00 -3.00D+00
                  CP: -3.00D+00  3.00D+00  1.58D+00  3.00D+00  3.00D+00
                  CP:  3.00D+00  1.22D+00  1.73D+00  6.16D-01
E= -1953.40631066710    Delta-E=       0.000063613358 Rises=F Damp=F
DIIS: error= 1.30D-04 at cycle  40 NSaved= 9.
NSaved= 9 IEnMin= 2 EnMin= -1953.40693610640    IErMin= 9 ErrMin= 1.30D-04
ErrMax= 1.30D-04  0.00D+00 EMaxC= 1.00D-01 BMatC= 1.08D-04 BMatP= 9.09D-05
IDIUse=3 WtCom= 9.99D-01 WtEn= 1.34D-03
Rare condition: small coef for last iteration:  0.000D+00
Coeff-Com:  0.426D+00-0.174D+01 0.321D+00 0.331D+01-0.361D+01 0.125D+01
Coeff-Com:  0.190D+01-0.210D+01 0.124D+01
Coeff-En: 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.000D+00
Coeff-En: 0.000D+00 0.000D+00 0.100D+01
Coeff:    0.426D+00-0.174D+01 0.321D+00 0.331D+01-0.361D+01 0.125D+01
Coeff:    0.190D+01-0.210D+01 0.124D+01
Gap=    0.042 Goal= None Shift= 0.000
Gap=    0.329 Goal= None Shift= 0.000
RMSDP=3.94D-03 MaxDP=2.02D+00 DE= 6.36D-05 OVMax= 2.38D-02

Cycle  41  Pass 1  IDiag  1:
Restarting incremental Fock formation.
E= -1953.40626958524    Delta-E=       0.000041081865 Rises=F Damp=F
DIIS: error= 1.31D-04 at cycle  41 NSaved=  10.
NSaved=10 IEnMin= 2 EnMin= -1953.40693610640    IErMin= 9 ErrMin= 1.30D-04
ErrMax= 1.31D-04  0.00D+00 EMaxC= 1.00D-01 BMatC= 1.12D-04 BMatP= 9.09D-05
IDIUse=3 WtCom= 9.99D-01 WtEn= 1.34D-03
Rare condition: small coef for last iteration:  0.000D+00
Coeff-Com:  0.451D+00-0.189D+01 0.360D+00 0.474D+01-0.506D+01 0.146D+01
Coeff-Com:  0.192D+01-0.225D+01 0.662D-01 0.121D+01
Coeff-En: 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.000D+00
Coeff-En: 0.000D+00 0.000D+00 0.000D+00 0.100D+01
Coeff:    0.451D+00-0.189D+01 0.360D+00 0.474D+01-0.506D+01 0.146D+01
Coeff:    0.192D+01-0.225D+01 0.662D-01 0.121D+01
Gap=    0.042 Goal= None Shift= 0.000
Gap=    0.329 Goal= None Shift= 0.000
RMSDP=4.25D-03 MaxDP=2.09D+00 DE= 4.11D-05 OVMax= 3.36D-02

Cycle  42  Pass 1  IDiag  1:
RMSU=  4.25D-03 CP:  1.00D+00
E= -1953.40616677231    Delta-E=       0.000102812925 Rises=F Damp=F
DIIS: error= 1.44D-04 at cycle  42 NSaved=  11.
NSaved=11 IEnMin= 2 EnMin= -1953.40693610640    IErMin= 9 ErrMin= 1.30D-04
ErrMax= 1.44D-04  0.00D+00 EMaxC= 1.00D-01 BMatC= 1.23D-04 BMatP= 9.09D-05
IDIUse=3 WtCom= 9.99D-01 WtEn= 1.34D-03
Rare condition: small coef for last iteration:  0.000D+00
Coeff-Com:  0.447D+00-0.188D+01 0.381D+00 0.401D+01-0.431D+01 0.134D+01
Coeff-Com:  0.192D+01-0.261D+01-0.706D+00 0.408D+01-0.166D+01
Coeff-En: 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.000D+00
Coeff-En: 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.100D+01
Coeff:    0.447D+00-0.188D+01 0.381D+00 0.401D+01-0.431D+01 0.134D+01
Coeff:    0.192D+01-0.261D+01-0.706D+00 0.408D+01-0.166D+01
Gap=    0.042 Goal= None Shift= 0.000
Gap=    0.329 Goal= None Shift= 0.000
RMSDP=2.39D-03 MaxDP=1.27D+00 DE= 1.03D-04 OVMax= 2.31D-02

Cycle  43  Pass 1  IDiag  1:
RMSU=  1.18D-03 CP:  1.00D+00  5.13D-01
E= -1953.40626625845    Delta-E=    -0.000099486139 Rises=F Damp=F
DIIS: error= 1.45D-04 at cycle  43 NSaved=  12.
NSaved=12 IEnMin= 2 EnMin= -1953.40693610640    IErMin= 9 ErrMin= 1.30D-04
ErrMax= 1.45D-04  0.00D+00 EMaxC= 1.00D-01 BMatC= 1.25D-04 BMatP= 9.09D-05
IDIUse=3 WtCom= 9.99D-01 WtEn= 1.34D-03
Coeff-Com:  0.568D+00-0.210D+01 0.381D+00 0.399D+01-0.427D+01 0.145D+01
Coeff-Com:  0.217D+01-0.379D+01-0.357D+00 0.548D+01-0.441D+01 0.189D+01
Coeff-En: 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.000D+00
Coeff-En: 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.000D+00 0.100D+01
Coeff:    0.567D+00-0.210D+01 0.381D+00 0.398D+01-0.427D+01 0.145D+01
Coeff:    0.217D+01-0.378D+01-0.356D+00 0.547D+01-0.440D+01 0.189D+01
Gap=    0.043 Goal= None Shift= 0.000
Gap=    0.329 Goal= None Shift= 0.000
RMSDP=3.04D-03 MaxDP=1.74D+00 DE=-9.95D-05 OVMax= 3.09D-02

Cycle  44  Pass 1  IDiag  1:
RMSU=  6.36D-04 CP:  1.00D+00  7.57D-02  2.96D+00

作者
Author: sobereva 时间: yesterday 16:54

nanokey 发表于 2026-2-20 13:09
sober老师好，其实就是类似计算垂直电子亲合能的过程，用中性结构计算阴离子状态的电子能量，总共25个原 ...

对于难收敛的情况，跑到43轮还没收敛是很正常的事。但从当前的趋势看继续跑下去收敛的可能性已经很低了
并且当前情况中性状态时是闭壳层计算，-1状态是非限制性开壳层，本来后者耗时就高得多得多

作者
Author: nanokey 时间: yesterday 23:37

sobereva 发表于 2026-2-20 16:54
对于难收敛的情况，跑到43轮还没收敛是很正常的事。但从当前的趋势看继续跑下去收敛的可能性已经很低了
...

好的，请问sober老师，这种情况我应该怎么优化调整呢？

作者
Author: wzkchem5 时间: 13 hour ago

nanokey 发表于 2026-2-20 23:37
好的，请问sober老师，这种情况我应该怎么优化调整呢？

按http://sobereva.com/61的方法逐个尝试，如果所有方法都无效，再来问，并说明哪些方法让收敛变好了，哪些让收敛变差了

作者
Author: nanokey 时间: 12 hour ago

wzkchem5 发表于 2026-2-21 10:25
按http://sobereva.com/61的方法逐个尝试，如果所有方法都无效，再来问，并说明哪些方法让收敛变好了，哪 ...

好的，感谢老师！

欢迎光临计算化学公社 (http://bbs.keinsci.com/)