[molpro-user] Error in excited state geometry optimization using TD-DFT

[Ralph Welsch]

Dear all,

I am trying to do some excited state geometry optimization using TD-DFT (see input file below). While doing that I encounter the following error:

 Quadratic Steepest Descent - Minimum Search
 ? Error
 ? Error in assigning eigenvector
 ? The problem occurs in dis1

I’m not really clear on what this error should tell me or where the problem is. I tried to change some convergence parameters, basis sets, functionals, etc., but that won’t help. 
Excluding some z-matrix coordinates from the minimum search space prevents the error, but optimizes to unphysical (energetically much higher) results and most of the time does not converge at all.

Any hints on how to resolve the problem are appreciated. If you need more information on my molar setup or the calculation, don’t hesitate to contact me.

Thanks for your help.

Best regards,
Ralph
——————————————————————————
memory,100,m

geom={
        ANGSTROM
        h1
        n1, h1, r01
        x1, n1, 2.0, h1, 90.0
        x2, n1, 2.0, h1, 90.0, x1, 90.0
        c1, n1, r02, h1, w02, x1, d02
        c2, n1, r03, h1, w03, x1, d03
        n2, c1, r04, n1, w04, x1, d04
        n3, c2, r05, n1, w05, x1, d05
        c3, c1, r06, n1, w06, x1, d06
        c4, c2, r07, n1, w07, x1, d07
        c5, c3, r10, c1, w10, x1, d10
        c6, c4, r11, c2, w11, x1, d11
        c7, c5, r14, c3, w14, x1, d14
        c8, c6, r15, c4, w15, x1, d15
        o1, c5, r12, c3, w12, c7, d12
        o2, c6, r13, c4, w13, c8, d13
        h2, o1, r16, c5, w16, c7, d16
        h3, o2, r17, c6, w17, c8, d17
        h4, c7, r18, c5, w18, x1, d18
        h5, c8, r19, c6, w19, x1, d19
        h9, n2, r08, c1, w08, x1, d08
        h10, n3, r09, c2, w09, x1, d09
}

 R01=                 1.01107463 ANGSTROM
 R02=                 1.3947 ANGSTROM
 W02=              -123.89 DEGREE
 D02=                -0.00000000 DEGREE
 R03=                 1.3947 ANGSTROM
 W03=               123.89 DEGREE
 D03=                -0.00000000 DEGREE
 R04=                 1.2736 ANGSTROM
 W04=              -130.80 DEGREE
 D04=                 0.00000000 DEGREE
 R05=                 1.2736 ANGSTROM
 W05=               130.80 DEGREE
 D05=                 0.00000000 DEGREE
 R06=                 1.4700 ANGSTROM
 W06=               105.51 DEGREE
 D06=                -0.00000000 DEGREE
 R07=                 1.4700 ANGSTROM
 W07=              -105.51 DEGREE
 D07=                -0.00000000 DEGREE
 R10=                 1.3805 ANGSTROM
 W10=              -129.75 DEGREE
 D10=                 0.00000000 DEGREE
 R11=                 1.3805 ANGSTROM
 W11=               129.75 DEGREE
 D11=                -0.00000000 DEGREE
 R14=                 1.4029 ANGSTROM
 W14=               116.84 DEGREE
 D14=                 0.00000000 DEGREE
 R15=                 1.4029 ANGSTROM
 W15=              -116.84 DEGREE
 D15=                 0.00000000 DEGREE
 R12=                 1.3543 ANGSTROM
 W12=              -122.53 DEGREE
 D12=                -0.00000000 DEGREE
 R13=                 1.3543 ANGSTROM
 W13=              -122.53 DEGREE
 D13=                -0.00000000 DEGREE
 R16=                 0.9743 ANGSTROM
 W16=              -108.51 DEGREE
 D16=                 0.00000000 DEGREE
 R17=                 0.9743 ANGSTROM
 W17=              -108.51 DEGREE
 D17=                 0.00000000 DEGREE
 R18=                 1.0841 ANGSTROM
 W18=              -118.50 DEGREE
 D18=                 0.00000000 DEGREE
 R19=                 1.0841 ANGSTROM
 W19=              -118.50 DEGREE
 D19=                 0.00000000 DEGREE
 R08=                 1.0193 ANGSTROM
 W08=               113.08 DEGREE
 D08=                 0.00000000 DEGREE
 R09=                 1.0193 ANGSTROM
 W09=               113.08 DEGREE
 D09=                 0.00000000 DEGREE

NOSYM
COSMO, EPSILON=32.7

basis={
set,orbital
default,6-311G**,h=6-311++G**,o=6-311++G**,n=6-311++G**                                                                                                                                                                                                                                             
set,mp2fit
default,vtz/mp2fit
}

gdirect
                                                                                                                                                                                            
rks, M06-2X; save,2100.2
e1=energy(1)
df-tddft,orb=2100.2,nexcit=1
diff=e1+omega(1)

put,xyz,input_orig_small.xyz
optg, MAXIT=100, proc=runtddft, variable=diff
ACTIVE, R01
ACTIVE, R02, W02, R03, W03
ACTIVE, R04, W04, R05, W05
ACTIVE, R06, W06, R07, W07
ACTIVE, R08, W08, R09, W09
ACTIVE, R10, W10, R11, W11
ACTIVE, R12, W12, R13, W13
ACTIVE, R14, W14, R15, W15
ACTIVE, R16, W16, R17, W17
ACTIVE, R18, W18, R19, W19
put,xyz,input_opti_small.xyz

runtddft={rks, M06-2X; save,2100.2; e1=energy(1); df-tddft,orb=2100.2,nexcit=1; diff=e1+omega(1);}