s~ ~~

~ {Afi" (

; BL{ -

- A (

o

+ B2­+_(A\

~J~lu3~ \v-~ sr',v> f

Ek ~:: - 3d',qC$ 3.1£r-t c.L~p-= - 3/1. M 2<-t l?

methylene.out Mon Mar 12 14:16:37 2007 1Welcome to Q-Chem

A Quantum Leap Into The Future Of Chemistry

Y. Shao, L. Fusti-Molnar, Y. Jung, J. Kussmann, C. Ochsenfeld,S. T. Brown, A. T. B. Gilbert, L. V. Slipchenko,S. V. Levchenko,D. P. O'Neill, R. A. DiStasio Jr., R. C. Lochan, T. Wang,G. J. O. Beran, N. A. Besley, J. M. Herbert, C. Y. Lin,T. Van Voorhis, S. H. Chien, A. Sodt, R. P. Steele,V. A. Rassolov, P. E. Maslen, P. P. Korambath, R. D. Adamson,B. Austin, J. Baker, E. F. C. Byrd, H. Dachsel, R. J. Doerksen,A. Dreuw, B. D. Dunietz, A. D. Dutoi, T. R. Furlani,S. R. Gwaltney, A. Heyden, S. Hirata, C.-P. Hsu, G. Kedziora,R. Z. Khalliulin, P. Klunzinger, A. M. Lee, M. S. Lee, W. Liang,I. Lotan, N. Nair, B. Peters, E. I. Proynov, P. A. Pieniazek,Y. M. Rhee, J. Ritchie, E. Rosta, C. D. Sherrill,A. C. Simmonett, J. E. Subotnik, H. L. Woodcock III,W. Zhang, A. T. Bell, A. K. Chakraborty, D. M. Chipman,F. J. Keil, A. Warshel, W. J. Hehre, H. F. Schaefer III,J. Kong, A. I. Krylov, P. M. W. Gill, M. Head-Gordon,Q-Chem, Version 3.0, Q-Chem, Inc., Pittsburgh, PA (2006)

NOok: ~ tvVlj~ Bi II SzIntel x86 Linux Version ~ ) s.ee.... 04.(f{~ 9j Oh..-

theFileMan (): MAXOPENFILES=974 MAX_SQ_NUM=16 w(.,ll!Al-r~, use.dz / J/ __£.. j('(!40l-(~Maximum size of a physical file is 2.0 GB, maximum size of a tmp-file is ~~trB

User input:

$moleculeo 3 -=::;- ... _. ---CH 1 rCHH 1 rCH 2 aHCH

rCHaHCH

$end

1.1167102.07

$remjobtype SPCORRELATION CCSDBASIS 6-31G*SCF_GUESS CORECC_NGUESS_SINGLES 4CC_DCONVERGENCE 8CC SPIN FLIP 1

CC:=NLOWSPIN [2,0,0,2] Get two 1"A1 and 1"B2 and 3"B2 -t~S-~$end 1---------------------~-~------------------------------------------------------~ IJ ~"'_ ~ ~ ~~.Wrltlng REM_CC_EA 0 .t..-.::, -'(~ ~ I~

ad- tk _~_._~~_.~_)~.(..+k L~ .~~~

Standard Nuclear Orientation (Angstroms)Atom X Y

use tighter convergence for optimization

Z

0.175558-0.526674-0.526674

0.0000000.0000000.000000

0.000000-0.8682680.868268

CHH

123

I

Molecular Point Group

Largest Abelian SubgroupNuclear Repulsion EnergyThere are 5 alpha and

C2v NOp = 4C2v NOp = 4

5.9912422132 hartrees3 beta electrons

methylene.out Mon Mar 12 14:16:37 2007 2

Requested basis set is 6-31G(d)There are 8 shells and 19 basis functions

Total memory of 2000MB is distributed as follows:QALLOC including MEM_STATIC uses 540MBMEM_STATIC is set to 241MBCCMAN JOB total tmp buffer size is 1060MBCC_TMPBUFFSIZE is set to 60MBCC_BLCK_TNSR_BUFFSIZE is set to 1000MB

Warning: actual memory use might exceed 2000MB

Total Memory LimitMega-Array SizeMEM_STATIC part

540 MB236 MB241 MB

HH

2)3 )

C ( 1)1.1167001.116700

Distance Matrix (Angstroms)H ( 2)

1.736536

Standard Electronic Orientation quadrupole field appliedNucleus-field energy = -0.0000000003 hartreesA cutoff of 1.0D-14 yielded 36 shell pairsThere are 217 function pairsSmallest overlap matrix eigenvalue = 3.08E-02Multipole matrices computed through 2nd orderGuess MOs from core Hamiltonian diagonalizationAn unrestricted Hartree-Fock SCF calculation will be

performed using Pulay DIIS extrapolationSCF converges when DIIS error is below 1.0E-08

Cycle Energy DIIS Error

1 -34.8288845040 2.60E-Ol2 -38.1950494695 8.91E-023 -38.8900109868 1.43E-024 -38.9023743357 2.59E-035 -38.9032299581 4.24E-046 -38.9033072003 1.18E-047 -38.9033217709 2.00E-058 -38.9033242548 1.15E-059 -38.9033252037 3.81E-06

10 -38.9033252298 6.19E-0711 -38.9033252300 1.37E-07

12 -38.9033252301 2.78E-08 J__:= ==~~~~==:~:=~: ~~=~~=~~_=onvergence criterion met

<SA2> = 2.0130SCF time: CPU 0.28 s wall 0.00 s

******************************************************* C C MAN *

**

*AnnaI.Krylov *

*C.David Sherrill *

*Steven R.Gwaltney *

*Edward F.C.Byrd *

*June2000 *

**

*AND *

**

* Sergey V.Levchenko ** Lyudrnila V.Slipchenko ** Tao Wang

**

Ana-Maria C.Cristian **

*

S~~~ ( S2..~

~ ~ ~tf-~'I'-

-tn r ~~ ~ 3Bc1-4-+-

methylene.out

*Mon Mar 12 14:16:37 2007

November 2003

3*

******************************************************

noooo

1.0E-02

1200

86

1.0E+00o7

113

no

50

no

o2

100016no

yes

O.OE+OOnono

885

1551

1.0E+00

CANONIZE_FREQ

PRECONV TZTHETAGRAD TRESH

BLCK_TNSR_BUFFSZNORBS_PER_BLOCKDO_PARENTHESIS_TINCL_VIRT_CORR

DOV_THRESHOPDM FROM GRADDO ED's CCDDO FOCK DIAG

E CONVERGZ CONVERGTHETA CONVERGRESET THETADIIS12 SWITCH

DIIS FREQDIIS MAX OVLP

no

nono

o1. 00

nono

yesyes60

1060no

yes

USER PARAMETERS:PRINTMAXITERT CONVERGTHETAGR CONVTHETA STEPSZDIIS MODEDIIS SIZEDIIS MIN OVLPDIIS STARTRESTART

REORTHOGONALIZE_MOPRECONV FROZENITERATE OV

PRECONV_TZ_EAHESS_THRESHUSE MP2-NO GUESS

DO QCCDSCF_ITERSCALE AMPL

CALC_SSQDO NUCLEAR GRADCANONIZE

CANONIZE_FINALTMP_MAXBUFSZTOT_MEM (ME)DO_DYNAMIC_CORRINCL_CORE_CORR

PARAMETERS FOR EOM CALCULATIONS:NLOWSPIN

2 002 0 0 0 0 0 0 0 0NHIGHSPIN

o 0 0 0 0 0 0 0 0 0 0 0DO_DYSON

0DO_CC_PROP

0PLOT_CC_DENSITIES 0DO_EXS_PROP

0DO_TRANS_PROP 0REF_SYM

1STATE_TO_OPT 0DO_SPIN_FLIP

yesDO PLAIN CIS

noDO CIS(D) noDO PLAIN CISD

noDO PLAIN CISDT noDO CC(2,3)

noIF_RESTR_TRIPLES noDO_SMALL_TRIPLES

0IF_1ITER_FULL_TRIPLES noPRECONV SD

0SPIN_FLIP_MS 1DO_IP_FILTER

noDO DIP

noDO_DISCNTD

noIF_RESTR_AMPL yes

301. OE-08

yes

PARAMETERS FOR DAVIDSONDMAXVECTORSDCONVERGENCE

NGUESS_SINGLESNGUESS_DOUBLESDO_APPR_DIAG

DIAGONALIZATION PROCEDURE:60 DMAXITER8 DTHRESHOLD4 PRECONV_SINGLESo PRECONV_DOUBLES

nono

Testing symmetry ... Orbitals in the original order:

Alpha MOs, Unrestricted-- Occupied --

-11.280 -0.945 -0.5581 A1 2 A1 1 B1

-- Virtual --

-0.5023 A1

-0.4171 B2

-- --- ---

methylene.out

Mon Mar 12 14:16:37 20074

0.262

0.2950.7170.7220.7230.9481.1041.1674 Al

2 Bl5 Al2 B23 Bl6 Al4 Bl7 Al1.895

1.8971.9132.2542.5124.3678 Al

3 B21 A29 Al5 Bl10 Al

Beta MOs, Unrestricted-- Occupied --

-11.228 -0.782 -0.5161 Al 2 Al 1 Bl

-- Virtual --

0.107 0.175 0.294 0.3473 Al 1 B2 4 Al 2 Bl1.154 1.207 2.025 2.0404 Bl 7 Al 8 Al 1 A2

Setting symmetry ... Orbitals willNo MO reordering is requested

0.751 0.8703 Bl 5 Al2.077 2.3703 B2 9 Albe reordered.

0.8962 B22.5865 Bl

1.0126 Al4.439

10 Al

The orbitals are ordered and numbered as follows:

t:~~) tl'sAlpha orbitals:

VV()Number EnergyTypeSymmetry:~

0

-11.280 AoeeAl ,flAOs wr/I( k1

-0.945AoeeAl I .s }-voW2

-0.502AoeeAl

~tLhu~1 L "'-3-0.558AoeeBl

4-0.417AoeeB2

~~~0

0.262AVIRTAl CcjLED~ - Q

1

0.717AVIRTAl2

0.948AVIRTAl3

1.167AVIRTAl4

1.895AVIRTAl5

2.254AVIRTAl6

4.367AVIRTAl7

1.913AVIRTA28

0.295AVIRTBl

~~9

0.723AVIRTB1

»)~~101.104AVIRTBl

112.512AVIRTBl

S 82-/ ~~f ;',-120.722AVIRTB2

131.897AVIRTB2 lSt

Beta orbitals:Number

EnergyType

Symmetry, \

1B~--+- ~~OC(0-11.228 AoeeAl {3 VI'~

1

-0.782AOeeAl2

-0.516AoeeBl3~tr-J:-O£{0-0 f'{

0

0.107AVIRTAl1

0.294AVIRTAl -fii2 0.870AVIRTAl ~\!3

1.012AVIRTAl4

1.207AVIRTAl

*l.Q\ \ace5

2.025AVIRTAl1-6

2.370AVIRTAl7

4.439AVIRTAl

1+-let (8

2.040AVIRTA29

0.347AVIRTBlI rL ~ '-Or10

0.751AVIRTBl11

1.154AVIRTBl

h",~S +t..~12

2.586AVIRTBl13

0.175AVIRTB2

#~ '"'14

0.896AVIRTB215

2.077AVIRTB2

~ ~~~MOLECULAR PARAMETERS:

methylene.out Mon Mar 12 14:16:37 20075

ORB SYMM INFO:POINT GROUP=C2v

NIRREPS=4

MOL ORB= 19IRREPS =

A1A2B1B2

ORBS PI =10153

DOCC

=2010SOCC

=1001

FDOCC

=0000RDOCC

=0000AAOCC

=3011BAOCC

=2010AAVIRT =

7142BAVIRT =

8143RUOCC

=0000FUOCC

=0000

IRREP MULT TABLE:0

1231

0322

3013

210

ORBSYM ALPHA= A1

A1A1B1B2A1A1A1A1A1A1

A1A2B1B1B1B1B2B2ORBSYM BETA = A1

A1B1A1A1A1A1A1A1A1A1

A2B1B1B1B1B2B2B2

BASIS ORBS

=19MOL ORBS=19

FROZEN OCC

=0FROZEN VIR=0

CaRR ORBS

=19CaRR SP ORBS =38NUM ALP ELEC =

5NUM BET ELEC =3NUM ALP EXPL =

5NUM BET EXPL =3NUM SO OCC

=8NUM SO VIR=30

NUM RESTR DOCC=0NUM RESTR DVIRT=0

ORBS PER BLCK =16RESTRICTED_REF =0

BLOCKING PARAMETERS:NUM ROCC BLOCKS =

0NUM AOCCBLOCKS=3NUM AVIRT BLOCKS=

4NUM RVIRT BLOCKS=0

ORBITALS/BLOCK =

31121071428143

BIRREP = A1

B1B2A1B1A1A1A2B1B2A1A2B1B2

Integral transformation job: CPU 0.36 s wall 1.00 sEHF = -38.903325230 EMP2 = -38.989915464

Beginning CC iterations

ItrlvarlDIEnergy IDelta_EIDelta_tIComments11 ccl-1 -39.00298704011.3E-02j7.0E-02121 ccl-1 -39.00624333313.3E-0312.8E-02131 ccl-1 -39.00731097911.1E-0311.5E-0214\ ccl+1 -39.00812757418.2E-0414.7E-03151 ccl+1 -39.00823739511.1E-0411.3E-03161 ccl+[ -39.00824986211.2E-0513.2E-04171 ccl+1 -39.00824838911.5E-0619.6E-05181 CCI+I -39.00824839S!5.9E-0912.8E-OSI91 ccl+1 -39.00824803813.6E-07j8.9E-061

101 ccl+1 -39.00824806913.1E-0812.2E-061111 ccj+\ -39.00824808SI1.6E-0817.1E-071

methylene.out Mon Mar 12 14:16:37 2007 6

12 CC +13 CC +14 CC +15 CC +

Calculation

-39.00824808511.7E-1011.8E-071-39.00824808113.7E-0914.2E-081-39.00824808214.3E-1011.4E-081-39.00824808213.4E-1°14.9E-091converged, 15 iterations

Largest T amplitudesLargest singles amplitudes:Value

i->a0.0229

1 ( A1)B ->o ( A1)B-0.0142

2( B1)B ->9( Bl)B-0.0131

2( B1)B ->11 ( B1)B-0.0090

1 ( A1)B ->4 ( A1)B-0.0080

2( B1)B ->10( B1)B

j -> a bA, 2 (B1 ) B -> 8 (B1 ) A, 9 (B1 ) BA, 1( A1 ) B -> O( A1 ) A, 13( B2 ) BA, 1( A1 ) B -> 8( B1 ) A, O( A1 ) BA, 4( B2 ) A -> 1( A1 ) A, 12( B2 ) AA, 2( B1 ) B -> 8( B1 ) A, 11( B1 ) B

-38. 903325230 .,~ 1_ u-.fJ .f) 1A~ rjsJ-38.989915464 ~ L Cs.(J:) ~ ------ a.J-0.104922852 ~/ ' .

-39.008248082 J -fht h;~ f.(JIL 3 ~ S~) 'IU- /J n D~ {;.+: ~ r}:X J-'k. Md' -L+CCSD or (V)OO-CCD job: CPU 0.83 s wall 1.00 s <: ~

Removing integral transformation files: 151 153 152 ~ •SOLVE EOM EQUATIONS FOR THE 2 LOWEST LOWSPIN STATES, TRANSITION OF A1 IRRE~

J {&.2( rlf ) >< A I +00....<- ~;'>; ~ ~

EHFEMP2

Correlation EnergyCCSD Total Energy

4 -> 272 -> 142 -> 157 -> 8

Largest doublesValue0.0484

-0.0337-0.0334-0.03190.0303

0.6234)0.6430)0.8296)0.8661)

3( B14( B23( B12 ( A13( B1

amplitudes:i

1:2 :3 :4 :

StateStateStateState

4 guess vectors generated

ItrlConvR ResNormR NVecslComments010 1.3E-01 4 I

11 0 9.3E-03 6 I

210 1.1E-03 8 I

310 1.8E-04 10 I41 0 3.0E-05 12 I51 0 4.9E-06 14 I61 0 6.3E-07 16 I71 0 5.5E-08 18 INSDavidsonRight<T>: :CalcCorrectionVec():

oot 0 is too small: 1.91E-09; II Res II =3 .94E-08NSDavidsonRight<T>::CalcCorrectionVec(): Warning! Scaled norm for9E-09; II Res II =7 .08E-08

Warning! Scaled norm for r

root 1 is too small: 2.7

2 lowest roots of symmetry Ai

Root 1 Conv-d yes Tot Ene= -39.007935653 hartree~(Ex Ene 0.0085 e~), U1A2=0.984255, U2A2=0.015745, \\Resll=5.6E-09Right U1:

Value a->

current subspace8 ITERATIONS

i

o1

81 2 15.7E-09 I 20 I CollapseDAVIDSON ITERATIONS CONVERGED,Excitation energies, hartree

o0.0003120.074550

State 1 :4 -> 14(0.5566)State

2 :2 -> 27(0.7097)State

3 :4 -> 15(0.7433)State

4 :1 -> 27(1.1481)

4 guess vectors generated

ItrlConvRIReSNOrmRlNVeCslComments01 0 11.4E-01 I 4 I11 0 18.9E-03 \ 6 I2\ 0 12.0E-03 I 8 I31 0 13.9E-04 I 10 141 0 16.2E-05 I 12 I

5 I 0 19.7E-06 I 14 I61 0 11.6E-06 I 16 I71 0 12.4E-07 I 18 !NSDavidsonRight<T>::CalcCorrectionVec():

oot 0 is too small: 4.24E-09; IIResll=1.20E-07

Root 2 Conv-d yes Tot Ene=026586, IIResll=5.8E-09Right U1:

Value0.6817

-0.67380.14100.1180

Warning! Scaled norm for r

i ->a

4( B2) A->13 ( B2)B

2 ( A1) A->O( A1)B

4( B2) A->14( B2) B

2 ( A1) A->2 ( A1)B

-lo ~A~~~ ~. r/oMen Mar 12 14,16,37 2007 zi 7 -f/IL -¢- 0.,..:' Lil f~ 4.

4 (B2 ) A -> 13 (B2 ) B +T ~t..2 (A1 ) A -> 0 (A1 ) B +- + ill Ii -~I~1 (A1 ) A -> 0 (A1 ) B C ( ~4 (B2 ) A -> 14 (B2 ) B ~~=J t-j (3- (l4S:::-{)~~~

-38.933698370 hartree (Ex Ene 2.0286 eV), U1A2=0.973414, U2A2=0.

-0.6779-0.6617-0.1666-0.1627

methylene. out

8\ 0 14.1E-08 I 20 INSDavidsonRight<T>: :CalcCorrectionVec():oot 0 is too small: 4.45E-10; IIResll=1.48E-08NSDavidsonRight<T>: :CalcCorrectionVec(): Warning! Scaled norm for9E-09; IIRes II =6.76E-08

Warning! Scaled norm for r

root 1 is too small: 2.8

9\ 1 16.4E-09 I 22 !NSDavidsonRight<T>: :CalcCorrectionVec(): Warning! Scaled norm for root 1 is too small: 3.64E-10; IIRes I 1=1.12E-08

101 2 11.0E-09 I 23 ICollapse current subspaceDAVIDSON ITERATIONS CONVERGED, 10 ITERATIONSExcitation energies, hartree

oo 0.0078991 0.183477

2 lowest roots of symmetry B2Root 1 Conv-d yes Tot Ene= -39.000349450 hartree (Ex Ene 0.2149 eV),025376, IIResll=8.9E-10Right U1:

Value

-0.9481-0.16950.1660

-0.0782

i ->a4( B2

) A->o ( A1

2( A1) A->13 ( B2

4( B2)A->2 ( A1

1( A1) A->13 ( B2

U1A2=0.974624,

0.4) it. . ~

i-Ct) i-t$J'-38.824771204 hartree (Ex Ene 4.9927 eV), U1A2=0.950101, U2A2=0.Root 2 Conv-d yes Tot Ene=

049899, IIResll=1.2E-09Right U1:

Value-0.9383-0.1853

i2 ( A12 ( A1

AA

->->->

a13 ( B214( B2

BB

Man Mar 12 14:16:37 2007methylene.out

0.1637-0.0754

4( B2 ) A1 (A1 ) A

->->

8

O( A113 ( B2

BB

EOM job: CPU 2.16 s wall 2.00 s

CCMAN JOB: ALL CPU 2.99 s wall 3.00 sCleaning up statics ....Analysis of SCF Wavefunction

Orbital Energies (a.u.) and Symmetries

0.9486 A11.1044 B1

0.8705 A10.7513 B1

Alpha MOs, Unrestricted-- Occupied --

-11.280 -0.945 -0.5021 A1 2 A1 3 A1

-- Virtual --0.262 0.7174 A1 5 A10.295 0.7232 B1 3 B1

Beta MOs, Unrestricted-- Occupied --

-11.228 -0.782 -0.5161 A1 2 A1 1 B1

-- Virtual --0.107 0.2943 A1 4 A12.040 0.3471 A2 2 B1

-0.5581 B1

1.1677 A12.5125 B1

1.0126 A11.1544 B1

-0.4171 B2

1.8958 A10.7222 B2

1.2077 A12.5865 B1

2.2549 A11.8973 B2

2.0258 A10.1751 B2

4.36710 A1

2.3709 A10.8962 B2

1.9131 A2

4.43910 A12.0773 B2

Mulliken Net Atomic Charges

Atom Charge (a .u .) Spin (a.u.)--------------------------------------------------------

1 C2 H3 H

Sum of atomic chargesSum of spin charges =

-0.3274250.1637120.163712

0.0000002.000000

2.190787-0.095393-0.095393

-----------------------------------------------------------------

Cartesian Multipole Moments-----------------------------------------------------------------

Charge (ESU x 10"10)0.0000Dipole Moment

(Debye)X

0.0000Y0.0000Z-0.6359Tot

0.6359

Quadrupole Moments(Debye-Ang)

XX-6.8991Xy0.0000yy-7.9624

xz0.0000YZ0.0000ZZ-6.8599

Octapole Moments(Debye-Ang"2 )

XXX0.0000XXy0.0000Xyy0.0000

yyy0.0000xxz-0.9219XYZ0.0000

YYZ-0.3142XZZ0.0000YZZ0.0000

ZZZ-1. 0862

Hexadecapole Moments(Debye-Ang"3)

methylene. out Mon Mar 12 14:16:37 20079

xxxx-14.1625XXXy0.0000XXyy-3.9763

Xyyy0.0000yyyy-8.4342XXXZ0.0000

XXYZ0.0000XYYZ0.0000YYYZ0.0000

XXZZ-3.7627XYZZ0.0000YYZZ-3.2461

XZZZ0.0000YZZZ0.0000ZZZZ-10.6276

Total job time: 4.00s(wall), 3.72s(cpu)

**************************************************************** Thank you very much for using Q-Chem. Have a nice day.

***

*************************************************************