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标题: 在平衡构型附近，指定CH4为Cs对称性报错 [打印本页]

作者
Author: jkr 时间: 2022-4-30 20:10
标题: 在平衡构型附近，指定CH4为Cs对称性报错
针对CH4体系，将某一个C-H键设置为1.1ang，其它键长键角保持甲烷的优化构型，希望将其视作Cs对称性进行计算，但是Molpro报错。经尝试，该键长设置为0.8、0.9、1.0、1.2、2.0、3.0 ang，均不会报错，好像只在平衡构型附近才会出错，请问这个问题要如何解决？

Molpro输入文件为：
-------------------------------------------------
***,CH4

symmetry,z
geometry={
angstrom
C
H1                C          B1
H2                C          B2 H1          A1
H3                C          B3 H2          A2 H1          D1
H4                C          B4 H2          A3 H1          D2
}

B1 =          1.100000000
B2 =          1.086000000
B3 =          1.086000000
B4 =          1.086000000
A1 =       109.4712206345
A2 =       109.4712206345
A3 =       109.4712206345
D1 =       -120.00000000
D2 =       120.00000060

basis=6-31G*

hf
--------------------输入文件结束----------------------

报错信息为：
-------------------------------------------------
ZSYMEL=Z

SETTING B1          =       1.10000000
SETTING B2          =       1.08600000
SETTING B3          =       1.08600000
SETTING B4          =       1.08600000
SETTING A1          =    109.47122063
SETTING A2          =    109.47122063
SETTING A3          =    109.47122063
SETTING D1          =    -120.00000000
SETTING D2          =    120.00000060
SETTING BASIS       = 6-31G*

Recomputing integrals since basis changed

Using spherical harmonics

The request for symmetry elements Z, cannot be honoured

Prototype coordinates
               1          2          3          4          5
      1    0.0000000 -0.0000005    1.3406801    0.5378542 -1.8785338
      2    0.0000000    0.0000000 -1.3951023    1.8586140 -0.4635117
      3 -0.0016622    2.0770365 -0.6857427 -0.6857429 -0.6857436
? Error
? Symmetry problem
? The problem occurs in zmatrix.f:zmat_orient
--------------------报错信息结束----------------------

作者
Author: qinjiu 时间: 2022-6-7 00:14
***,CH4

noorient
symmetry,x
geometry={
angstrom
C
H1                C          B1
H2                C          B2 H1          A1
H3                C          B3 H2          A2 H1          D1
H4                C          B4 H2          A3 H1          D2
}

B1 =          1.100000000
B2 =          1.086000000
B3 =          1.086000000
B4 =          1.086000000
A1 =       109.4712206345
A2 =       109.4712206345
A3 =       109.4712206345
D1 =       -120.00000000
D2 =       120.00000060

basis=6-31G*

hf
Commands  initialized (763), CPU time= 0.01 sec, 617 directives.
Default parameters read. Elapsed time= 0.06 sec

Checking input...
Passed
1

Variable memory set to 8000000 words,  buffer space

ZSYMEL=X

SETTING B1          =       1.10000000
SETTING B2          =       1.08600000
SETTING B3          =       1.08600000
SETTING B4          =       1.08600000
SETTING A1          =    109.47122063
SETTING A2          =    109.47122063
SETTING A3          =    109.47122063
SETTING D1          =    -120.00000000
SETTING D2          =    120.00000060
SETTING BASIS       = 6-31G*

Recomputing integrals since basis changed

Using spherical harmonics

Library entry C    S 6-31G             selected for orbital group  1
Library entry C    P 6-31G             selected for orbital group  1
Library entry C    D 6-31G*             selected for orbital group  1
Library entry H    S 6-31G             selected for orbital group  2

PROGRAM * SEWARD (Integral evaluation for generally contracted gaussian basis sets)    Author: Roland Lindh, 1990

Geometry written to block  1 of record 700

Point group  Cs

ATOMIC COORDINATES

NR  ATOM CHARGE    X             Y             Z

1  C    6.00 0.000000000 0.000000000 0.000000000
2  H1    1.00 0.000000000 0.000000000 2.078698737
3  H2    1.00 0.000000000 1.934872852 -0.684080857
4  H3    1.00 1.675649038 -0.967436429 -0.684080865
5  H4    1.00 -1.675649038 -0.967436429 -0.684080865

Bond lengths in Bohr (Angstrom)

1-2  2.078698737  1-3  2.052242571  1-4  2.052242571  1-5  2.052242571
   ( 1.100000000)    ( 1.086000000)    ( 1.086000000)    ( 1.086000000)

Bond angles

  2-1-3  109.47122063 2-1-4  109.47122088 2-1-5  109.47122088 3-1-4  109.47122063

  3-1-5  109.47122063 4-1-5  109.47122014

NUCLEAR CHARGE:                10
NUMBER OF PRIMITIVE AOS:       44
NUMBER OF SYMMETRY AOS:          43
NUMBER OF CONTRACTIONS:          22 ( 16A'  + 6A"  )
NUMBER OF CORE ORBITALS:          1 ( 1A'  + 0A"  )
NUMBER OF VALENCE ORBITALS:       8 ( 6A'  + 2A"  )

NUCLEAR REPULSION ENERGY 13.44192301

Eigenvalues of metric

      1 0.205E-01 0.730E-01 0.749E-01 0.294E+00 0.299E+00 0.387E+00 0.478E+00 0.578E+00
      2 0.730E-01 0.294E+00 0.578E+00 0.100E+01 0.112E+01 0.251E+01

Contracted 2-electron integrals neglected if value below    1.0D-11
AO integral compression algorithm  1 Integral accuracy    1.0D-11

   0.262 MB (compressed) written to integral file (100.0%)

NUMBER OF SORTED TWO-ELECTRON INTEGRALS:    18115.    BUFFER LENGTH:  32768
NUMBER OF SEGMENTS: 1  SEGMENT LENGTH:    18115    RECORD LENGTH: 524288

Memory used in sort:    0.58 MW

SORT1 READ    23390. AND WROTE    14627. INTEGRALS IN    1 RECORDS. CPU TIME:    0.00 SEC, REAL TIME:    0.00 SEC
SORT2 READ    14627. AND WROTE    18115. INTEGRALS IN    1 RECORDS. CPU TIME:    0.00 SEC, REAL TIME:    0.01 SEC

FILE SIZES: FILE 1: 30.3 MBYTE,  FILE 4:    4.2 MBYTE, TOTAL:    34.5 MBYTE

OPERATOR DM    FOR CENTER  0  COORDINATES: 0.000000 0.000000 0.000000

**********************************************************************************************************************************
DATASETS  * FILE NREC LENGTH (MB) RECORD NAMES
            1    19    30.10    500    610    700    900    950    970    1000    129    960    1100
                                       VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS    P2S ABASIS    S
                                       1400    1410    1200    1210    1080    1600    1650    1300    1700
                                       T       V    H0    H01    AOSYM    SMH MOLCAS ERIS    OPER

PROGRAMS *       TOTAL    INT
CPU TIMES  *       0.28    0.19
REAL TIME  *       0.33 SEC
DISK USED  *       34.81 MB
**********************************************************************************************************************************

PROGRAM * RHF-SCF (CLOSED SHELL)    Authors: W. Meyer, H.-J. Werner

NUMBER OF ELECTRONS:    5+ 5-
CONVERGENCE THRESHOLDS: 1.00E-05 (Density) 1.00E-07 (Energy)
MAX. NUMBER OF ITERATIONS:    60
INTERPOLATION TYPE:          DIIS
INTERPOLATION STEPS:             2 (START)    1 (STEP)
LEVEL SHIFTS:                0.00 (CLOSED)  0.00 (OPEN)

Orbital guess generated from atomic densities. Full valence occupancy: 7 2

Molecular orbital dump at record       2100.2

Initial occupancy: 4 1

ITERATION DDIFF       GRAD          ENERGY       2-EL.EN.          DIPOLE MOMENTS       DIIS ORB.
1    0.000D+00    0.000D+00    -40.17387671    53.192586 0.00000 -0.00000 0.00714 0 start
2    0.000D+00    0.166D-01    -40.19205261    51.736457 0.00000 -0.00000 -0.00316 1 diag
3    0.171D-01    0.650D-02    -40.19441263    52.208203 0.00000 -0.00000 -0.00328 2 diag
4    0.498D-02    0.141D-02    -40.19465227    52.151155 0.00000 -0.00000 -0.00460 3 diag
5    0.278D-02    0.144D-03    -40.19465440    52.152650 0.00000 -0.00000 -0.00478 4 diag
6    0.443D-03    0.427D-05    -40.19465440    52.152744 0.00000 -0.00000 -0.00479 5 diag
7    0.118D-04    0.362D-06    -40.19465440    52.152738 0.00000 -0.00000 -0.00479 6 diag
8    0.560D-06    0.617D-07    -40.19465440    52.152738 0.00000 -0.00000 -0.00479 0 orth

Final occupancy: 4 1

!RHF STATE  1.1 Energy             -40.194654400713
Nuclear energy                      13.44192301
One-electron energy                -79.71294617
Two-electron energy                26.07636876
Virial quotient                      -0.99928741
!RHF STATE  1.1 Dipole moment       0.00000000 -0.00000000 -0.00479491
Dipole moment /Debye                0.00000000 -0.00000000 -0.01218665

Orbital energies:

      1.1       2.1       3.1       4.1       5.1       6.1
-11.203613 -0.942283 -0.545919 -0.542371    0.256021    0.324306

      1.2       2.2       3.2
   -0.545919    0.327106    0.728723

HOMO    4.1 -0.542371 =    -14.7587eV
LUMO    5.1    0.256021 =    6.9667eV
LUMO-HOMO       0.798392 =    21.7254eV

**********************************************************************************************************************************
DATASETS  * FILE NREC LENGTH (MB) RECORD NAMES
            1    19    30.10    500    610    700    900    950    970    1000    129    960    1100
                                       VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS    P2S ABASIS    S
                                       1400    1410    1200    1210    1080    1600    1650    1300    1700
                                       T       V    H0    H01    AOSYM    SMH MOLCAS ERIS    OPER

            2    4       2.80    700    1000    520    2100
                                       GEOM    BASIS MCVARS    RHF

PROGRAMS *       TOTAL HF-SCF    INT
CPU TIMES  *       0.40    0.12    0.19
REAL TIME  *       0.46 SEC
DISK USED  *       34.81 MB
**********************************************************************************************************************************
Molecular orbitals read from record    2100.2  Type=RHF/CANONICAL (state 1.1)
Occupation numbers read from record    2100.2  Type=RHF/RHF (state 1.1)
Orbital energies read from record    2100.2  Type=RHF/CANONICAL (state 1.1)
Redundancy group numbers read from rec  2100.2  Type=RHF/RHF (state 1.1)

HF/6-31G* energy= -40.194654400713

      HF-SCF
-40.19465440
**********************************************************************************************************************************
Molpro calculation terminated

作者
Author: 北大-陶豫 时间: 2022-6-7 10:09
我不懂Molpro，但是甲烷只固定一个键长的话对称性是C3v不是Cs啊

作者
Author: qinjiu 时间: 2022-6-28 18:52

北大-陶豫发表于 2022-6-7 10:09
我不懂Molpro，但是甲烷只固定一个键长的话对称性是C3v不是Cs啊

Molpro可以用低对称性的阿贝尔子群计算高对称性的分子，比如C2v算C∞v，D∞v，最后再把A1A2B1B2通过一些规则组合成Sigma+那些

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