1

Electronic Supplementary Information (ESI)

Infrared Spectroscopy of Hydrated Polycyclic Aromatic Hydrocarbon Cations:

Naphthalene+-Water

Kuntal Chatterjee and Otto Dopfer*

Institut für Optik und Atomare Physik, Technische Universität Berlin, Hardenbergstr. 36, 10623 Berlin, Germany.

* Corresponding author: Fax: (+49) 30-31423018, E-Mail: dopfer@physik.tu-berlin.de

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics.This journal is © the Owner Societies 2017

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Table S1. Comparison of calculated (B3LYP-D3/aug-cc-pVTZ) and observed geometrical parameters (in Å and degree)

for neutral and ionized naphthalene.

Np

calculated

Np

experiment a

Np

experiment b

Np+

calculated

C9-C10 1.4282 1.412(8) 1.421 1.4263

C9-C1 1.4161 1.422(3) 1.424 1.4080

C1-C2 1.3706 1.381(2) 1.377 1.4005

C2-C3 1.4122 1.417(4) 1.411 1.3859

C1-H 1.0827 1.092(1) 1.095 1.0820

C2-H 1.0817 1.092(1) 1.098 1.0807

C1-C9-C10 118.9 119.5(3) 119.0 119.0

C9-C1--C2 120.9 120.2 120.8

C1-C2-C3 120.3 120.5 120.2

H-C1-C9 118.8 117.0 119.4

H-C2-C1 120.1 119.9 119.7

a Experimental geometries obtained in gas phase from electron diffraction (Ref. Ketkar et al, 1981). b Experimental geometries in solid phase from X-ray diffraction (Ref. Ponomarev et al., 1976).

Table S2. C-H stretch frequencies in cm-1 of Np, Np+, and Np+-Ar calculated at the B3LYP-D3/aug-cc-pVTZ level (IR

intensities in km mol-1 and symmetry species in parentheses).

Np Np+ Np+-Ar

D2h D2h Cs

νCH [cm-1] 3070 (0, ag)

3069 (37, b2u)

3057 (51, b1u)

3056 (0, b3g)

3045 (0, ag)

3042 (1, b2u)

3040 (5, b1u)

3038 (0, b3g)

3091 (0, ag)

3091 (2, b2u)

3081 (1, b1u)

3080 (0, b3g)

3070 (0, ag)

3068 (1, b2u)

3067 (0.3, b1u)

3065 (0, b3g)

3091 (0.02, a’)

3091 (2, a’)

3081 (1, a”)

3080 (0.002, a”)

3069 (0, a’)

3067 (0.1, a’)

3066 (0.3, a”)

3063 (0, a”)

νCH (aver) [cm-1] a 3052 3077 3076

a Averaged value.

3

Table S3. CH stretch frequencies of Bz, Bz+, and Bz+-Ar obtained at the B3LYP-D3/aug-cc-pVTZ level.a

Bz Bz+ Bz+-Ar

D6h D2h Cs

νCH [cm-1] 3074 (0, a1g)

3064 (34, e1u)

3064 (34, e1u)

3049 (0, e2g)

3049 (0, e2g)

3039 (0, b1u)

3097(0, ag)

3094 (17, b2u)

3086 (9, b1u)

3082 (0, b3g)

3072 (0, ag)

3069 (2, b1u)

3098 (0.1, a’)

3094 (15, a”)

3087 (8, a’)

3083 (0.01, a”)

3076 (0.1, a’)

3069 (1, a’)

νCH (aver) [cm-1] b 3057 3083 3085

a Values in parentheses are IR intensities in km mol-1 and vibrational symmetry. b Averaged value.

Table S4. Selected vibrational, and energetic parameters of Np+-H2O(12), Np+-H2O(23), Np+-H2O(12)-Ar, and

Np+-H2O(23)-Ar in the D0 state obtained at the B3LYP-D3/aug-cc-pVTZ level.

Np+-H2O(12) Np+-H2O(23) Np+-H2O(12)-Ar Np+-H2O(23)-Ar

Cs C2v C1 C1

ν1 [cm-1] a 3646 (31, a’) 3646 (31, a1) 3646 (31) 3646 (31)

ν3 [cm-1] a 3733 (91, a”) 3734 (90, b1) 3733 (90) 3734 (90)

νCH [cm-1] a 3095 (13, a’)

3090 (0.4, a’)

3081 (4, a’)

3079 (0.1, a’)

3074 (8, a’)

3068 (0.2, a’)

3065 (0.3, a’)

3063 (0, a’)

3096 (30, a1)

3089 (0.5, a1)

3087 (0.1, b2)

3079 (0.1, b2)

3066 (0.01, a1)

3064 (2, a1)

3064 (0.02, b2)

3062 (0.02, b2)

3095 (13)

3090 (0.4)

3081 (4)

3079 (0.1)

3074 (9)

3067 (0.1)

3065 (0.03)

3063 (0.2)

3097 (29)

3090 (0.5)

3088 (0.2)

3080 (0.1)

3067 (0.02)

3065 (1)

3065 (0.3)

3063 (0.02)

νCH (aver) [cm-1] b 3077 3076 3077 3077

D0 [cm-1] c 2458 (2907) 2340 (2783) 2995 (3509) 2892 (3395)

a Values in parentheses are IR intensities in km mol-1 and vibrational symmetry. b Averaged value. c Interaction energies (De) in parenthesis.

4

Figure Captions

Figure S1. HOMO of Np and Np+ calculated at the B3LYP-D3/aug-cc-pVTZ level.

Figure S2. NBO charge distribution (in e) for Np, Np+, Np+-H2O(18), Np+-H2O(12), Np+-H2O(23), Np+-H2O(π), and

Bz+-H2O(12) calculated at the B3LYP-D3/aug-cc-pVTZ level.

Figure S3. Linear IR absorption spectra of Np, Np+, Bz, and Bz+ calculated at the B3LYP-D3/aug-cc-pVTZ level.

Figure S4. Structures of Np+-Ar and Bz+-Ar calculated at the B3LYP-D3/aug-cc-pVTZ level. Binding energies (D0) and

bond lengths (R) are given in cm-1 and Å, respectively.

Figure S5. Structures of neutral Np-H2O and Bz-H2O calculated at the B3LYP-D3/aug-cc-pVTZ level. Binding energies

(D0) and bond lengths (R) are given in cm-1 and Å, respectively.

Figure S6. Structures of Bz+-H2O(12) and Bz+-H2O(π) calculated at the B3LYP-D3/aug-cc-pVTZ level. Binding energies

(D0) and bond lengths are given in cm-1 and Å, respectively. Numbers in parentheses correspond to relative energies (E0)

and relative free energies (G).

Figure S7. Natural bond orbitals of Np+-H2O(18), Np+-H2O(12), Np+-H2O(23), and Bz+-H2O(12). The phases of the NBOs

are indicated by blue and yellow. All clusters show an in-phase overlap between the lone pair orbital of H2O and the

antibonding σ* orbital of the CH groups.

Figure S8. Structures of Np+-H2O(18)-Ar, Np+-H2O(12)-Ar, and Np+-H2O(23)-Ar calculated at the B3LYP-D3/aug-cc-

pVTZ level. Binding energies (D0), bond lengths, and bond angles are given in cm-1, Å, and degrees, respectively.

Numbers in parentheses correspond to relative energies (E0) and relative free energies (G).

Figure S9. Comparison of IRPD spectra of Np+-H2O-Ar recorded in the Ar and Ar+H2O loss channels with linear IR

absorption spectra of Np+-H2O(18)-Ar, Np+-H2O(12)-Ar, and Np+-H2O(23)-Ar computed at the B3LYP-D3/aug-cc-pVTZ

level.

Figure S1

HOMO (Np) HOMO (Np+)

Figure S2

Figure S3

Figure S4

Figure S5

Figure S6

Figure S7

Np+-H2O(18) Np+-H2O(12)

Np+-H2O(23) Bz+-H2O(12)

Figure S8

Figure S9

5

CartesianCoordinatesandAbsoluteEnergies

Ar

HF=-527.5600021(Hartree/particle)

H2O

O0.000000000.000000000.11696500H0.000000000.76345100-0.46786000H0.00000000-0.76345100-0.46786000Zero-pointcorrection=0.021244(Hartree/Particle)ThermalcorrectiontoEnergy=0.024079ThermalcorrectiontoEnthalpy=0.025023ThermalcorrectiontoGibbsFreeEnergy=0.003602Sumofelectronicandzero-pointEnergies=-76.444961SumofelectronicandthermalEnergies=-76.442126SumofelectronicandthermalEnthalpies=-76.441181SumofelectronicandthermalFreeEnergies=-76.462602

6

NpC0.000000002.423809000.70608000C0.000000001.240382001.39746300C0.000000000.000000000.71411700C0.000000000.00000000-0.71411700C0.000000001.24038200-1.39746300C0.000000002.42380900-0.70608000H0.00000000-1.239165002.48018400H0.000000003.364347001.24034800H0.000000001.239165002.48018400C0.00000000-1.240382001.39746300C0.00000000-1.24038200-1.39746300H0.000000001.23916500-2.48018400H0.000000003.36434700-1.24034800C0.00000000-2.42380900-0.70608000C0.00000000-2.423809000.70608000H0.00000000-1.23916500-2.48018400H0.00000000-3.36434700-1.24034800H0.00000000-3.364347001.24034800

Zero-pointcorrection=0.147321(Hartree/Particle)ThermalcorrectiontoEnergy=0.154114ThermalcorrectiontoEnthalpy=0.155058ThermalcorrectiontoGibbsFreeEnergy=0.117424Sumofelectronicandzero-pointEnergies=-385.892955SumofelectronicandthermalEnergies=-385.886162SumofelectronicandthermalEnthalpies=-385.885217SumofelectronicandthermalFreeEnergies=-385.922851

7

Np+

C0.000000002.441800000.69292400C0.000000001.230960001.39671200C0.000000000.000000000.71315400C0.000000000.00000000-0.71315400C0.000000001.23096000-1.39671200C0.000000002.44180000-0.69292400H0.00000000-1.237831002.47872900H0.000000003.376044001.23605900H0.000000001.237831002.47872900C0.00000000-1.230960001.39671200C0.00000000-1.23096000-1.39671200H0.000000001.23783100-2.47872900H0.000000003.37604400-1.23605900C0.00000000-2.44180000-0.69292400C0.00000000-2.441800000.69292400H0.00000000-1.23783100-2.47872900H0.00000000-3.37604400-1.23605900H0.00000000-3.376044001.23605900

Zero-pointcorrection=0.146926(Hartree/Particle)ThermalcorrectiontoEnergy=0.153953ThermalcorrectiontoEnthalpy=0.154897ThermalcorrectiontoGibbsFreeEnergy=0.116160Sumofelectronicandzero-pointEnergies=-385.604269SumofelectronicandthermalEnergies=-385.597242SumofelectronicandthermalEnthalpies=-385.596298SumofelectronicandthermalFreeEnergies=-385.635034

8

Np+-H2O(18)

C0.000000000.000000000.15285200C0.000000000.00000000-1.27379600C0.000000001.228939000.84111800C0.000000001.23131500-1.95631000C0.00000000-1.228939000.84111800C0.00000000-1.23131500-1.95631000C0.000000002.439220000.13473400C0.000000002.44073000-1.25130900C0.00000000-2.439220000.13473400C0.00000000-2.44073000-1.25130900H0.000000001.221087001.92386200H0.000000001.23970000-3.03843300H0.00000000-1.221087001.92386200H0.00000000-1.23970000-3.03843300H0.000000003.373544000.67789500H0.000000003.37508600-1.79434100H0.00000000-3.373544000.67789500H0.00000000-3.37508600-1.79434100O0.000000000.000000003.90477500H-0.763758000.000000004.49192900H0.763758000.000000004.49192900

Zero-pointcorrection=0.170542(Hartree/Particle)ThermalcorrectiontoEnergy=0.181398ThermalcorrectiontoEnthalpy=0.182342ThermalcorrectiontoGibbsFreeEnergy=0.133463Sumofelectronicandzero-pointEnergies=-462.061863SumofelectronicandthermalEnergies=-462.051007SumofelectronicandthermalEnthalpies=-462.050063SumofelectronicandthermalFreeEnergies=-462.098942

9

Np+-H2O(12)

C-2.40796600-1.846485000.00000000C-2.51091200-0.450311000.00000000C-1.359113000.355922000.00000000C-0.07582400-0.268416000.00000000C0.00000000-1.673597000.00000000C-1.16154300-2.453874000.00000000H-2.403057002.243327000.00000000H-3.30548300-2.448405000.00000000H-3.487339000.016085000.00000000C-1.432866001.763791000.00000000C1.077681000.538780000.00000000H0.97072600-2.151617000.00000000H-1.08253500-3.531610000.00000000C0.974982001.937424000.00000000C-0.270734002.544132000.00000000H2.063557000.093215000.00000000H1.885034002.519498000.00000000H-0.351779003.621802000.00000000O4.110223001.355225000.00000000H4.692331001.435367000.76301600H4.692331001.43536700-0.76301600Zero-pointcorrection=0.170217(Hartree/Particle)ThermalcorrectiontoEnergy=0.181230ThermalcorrectiontoEnthalpy=0.182174ThermalcorrectiontoGibbsFreeEnergy=0.131921Sumofelectronicandzero-pointEnergies=-462.060428SumofelectronicandthermalEnergies=-462.049415SumofelectronicandthermalEnthalpies=-462.048471SumofelectronicandthermalFreeEnergies=-462.098724

10

Np+-H2O(23)

C0.000000000.71337300-0.69142500C0.00000000-0.71337300-0.69142500C0.000000001.396001000.54187000C0.00000000-1.396001000.54187000C0.000000001.39604000-1.92107800C0.00000000-1.39604000-1.92107800C0.000000000.693292001.75283000C0.00000000-0.693292001.75283000C0.000000000.69299500-3.13186200C0.00000000-0.69299500-3.13186200H0.000000002.478292000.54776200H0.00000000-2.478292000.54776200H0.000000002.47814700-1.92816000H0.00000000-2.47814700-1.92816000H0.000000001.217255002.69756700H0.00000000-1.217255002.69756700H0.000000001.23656800-4.06581400H0.00000000-1.23656800-4.06581400O0.000000000.000000004.83870300H0.762911000.000000005.42634500H-0.762911000.000000005.42634500Zero-pointcorrection=0.170186(Hartree/Particle)ThermalcorrectiontoEnergy=0.181201ThermalcorrectiontoEnthalpy=0.182145ThermalcorrectiontoGibbsFreeEnergy=0.132647Sumofelectronicandzero-pointEnergies=-462.059894SumofelectronicandthermalEnergies=-462.048879SumofelectronicandthermalEnthalpies=-462.047935SumofelectronicandthermalFreeEnergies=-462.097433

11

Np+-H2O(π)

C-2.33068200-0.06321200-0.61387100C-1.17435500-0.63041600-1.16109900C-0.01570800-0.79301600-0.38221300C-0.03049000-0.370484000.97918000C-1.203603000.197220001.50573600C-2.345098000.347874000.71032200H1.18234600-1.67178800-1.94349900H-3.212463000.05189300-1.22789100H-1.16860300-0.94787900-2.19551300C1.16173200-1.35590500-0.90886700C1.13262700-0.528902001.75552200H-1.220860000.521396002.53795300H-3.238151000.785185001.13347800C2.28776400-1.101838001.21013300C2.30207700-1.51231800-0.11176800H1.13027400-0.203151002.78729200H3.16763100-1.219344001.82638300H3.19322800-1.95289600-0.53545500O1.917078001.79503500-0.43676300H1.478384002.61405000-0.68988300H2.856338001.99826700-0.49904000Zero-pointcorrection=0.169801(Hartree/Particle)ThermalcorrectiontoEnergy=0.181111ThermalcorrectiontoEnthalpy=0.182055ThermalcorrectiontoGibbsFreeEnergy=0.130087Sumofelectronicandzero-pointEnergies=-462.058102SumofelectronicandthermalEnergies=-462.046792SumofelectronicandthermalEnthalpies=-462.045847SumofelectronicandthermalFreeEnergies=-462.097816

12

Np+-H2O(18)-Ar

C1.14098100-2.23018000-0.61608900C1.63019200-1.09247300-1.26828000C0.827102000.05388700-1.41569300C-0.499195000.04138800-0.89147300C-0.97104800-1.11480700-0.24079000C-0.14796900-2.24089400-0.10701600H2.303706001.23461500-2.45228600H1.77449100-3.09939400-0.51126900H2.63837600-1.08970300-1.66134900C1.297788001.21657500-2.05376100C-1.302942001.18991700-1.02476100H-1.97781600-1.115767000.15762400H-0.52436300-3.119519000.39727000C-0.806962002.33412800-1.66366100C0.481661002.34759500-2.17367900H-2.307520001.17404300-0.62122300H-1.435830003.20813600-1.75639000H0.862726003.23102700-2.66586000O-3.963680000.035248000.55432700H-4.78725500-0.227073000.12892700H-4.218376000.301044001.44456500Ar1.462015000.898889001.96532200Zero-pointcorrection=0.170774(Hartree/Particle)ThermalcorrectiontoEnergy=0.184264ThermalcorrectiontoEnthalpy=0.185208ThermalcorrectiontoGibbsFreeEnergy=0.125481Sumofelectronicandzero-pointEnergies=-989.624370SumofelectronicandthermalEnergies=-989.610880SumofelectronicandthermalEnthalpies=-989.609936SumofelectronicandthermalFreeEnergies=-989.669663

13

Np+-H2O(12)-Ar

C-2.97280200-1.08541800-0.15709700C-2.36673700-0.620653001.01618400C-0.96684000-0.562782001.12797400C-0.16541800-0.987475000.02685400C-0.79885600-1.45195500-1.14014600C-2.19454500-1.49810100-1.22772800H-0.932685000.238083003.12998100H-4.05082800-1.12060900-0.22380900H-2.98106300-0.299176001.84696600C-0.33008700-0.087013002.29192400C1.23622100-0.918833000.13439500H-0.19497500-1.77364800-1.97835500H-2.66276900-1.85657200-2.13326300C1.84362300-0.438916001.30361000C1.06584500-0.026758002.37345400H1.86881900-1.23144000-0.68563400H2.92241300-0.399885001.34338200H1.532168000.344074003.27506400O4.27325300-1.14938700-0.63766300H4.83334400-1.92916500-0.56196700H4.80097600-0.51488100-1.13401900Ar-0.095259002.49683500-0.55863000Zero-pointcorrection=0.170514(Hartree/Particle)ThermalcorrectiontoEnergy=0.184132ThermalcorrectiontoEnthalpy=0.185076ThermalcorrectiontoGibbsFreeEnergy=0.124842Sumofelectronicandzero-pointEnergies=-989.622878SumofelectronicandthermalEnergies=-989.609259SumofelectronicandthermalEnthalpies=-989.608315SumofelectronicandthermalFreeEnergies=-989.668549

14

Np+-H2O(23)-Ar

C-3.04288700-1.060749000.55314700C-1.83693500-1.036968001.26390100C-0.60478100-0.974544000.58971300C-0.59653600-0.93768600-0.83612400C-1.82082900-0.96498600-1.52687200C-3.03489600-1.02494700-0.83227600H0.62188400-0.960383002.36267500H-3.97941700-1.107063001.09027800H-1.85010100-1.063451002.34559600C0.62264400-0.934764001.28071700C0.63886800-0.86272900-1.50983100H-1.82148600-0.93608900-2.60859000H-3.96515200-1.04313900-1.38185400C1.84413400-0.82136600-0.79892500C1.83607600-0.857226000.58703000H0.65080600-0.83309200-2.59163300H2.79062400-0.75987900-1.31599900H2.77650000-0.823089001.11752400O4.92191000-0.65580200-0.08421900H5.55757100-1.37892700-0.10354400H5.458935000.14281900-0.05058100Ar-0.362836002.513042000.02358100

Zero-pointcorrection=0.170460(Hartree/Particle)ThermalcorrectiontoEnergy=0.184109ThermalcorrectiontoEnthalpy=0.185053ThermalcorrectiontoGibbsFreeEnergy=0.125058Sumofelectronicandzero-pointEnergies=-989.622411SumofelectronicandthermalEnergies=-989.608762SumofelectronicandthermalEnthalpies=-989.607818SumofelectronicandthermalFreeEnergies=-989.667812

15

Np-H2O

C-2.23903400-0.16320000-0.60308700C-1.09966100-0.66832000-1.17347300C0.08276500-0.82992500-0.41108900C0.07024200-0.459763000.96873800C-1.124358000.057020001.52712200C-2.251341000.203394000.76076700H1.29442800-1.59953500-2.02203700H-3.13473000-0.04148100-1.19691700H-1.08757200-0.94603300-2.21962700C1.28361200-1.32603500-0.97487000C1.25840200-0.602633001.72630100H-1.131968000.340964002.57167600H-3.156416000.602457001.19822800C2.40590600-1.081956001.14941800C2.41857100-1.44718400-0.21572900H1.24935500-0.315922002.76994300H3.30851000-1.179899001.73704400H3.33089000-1.82128300-0.65996800O1.625960002.22526400-0.44605100H2.058293001.39235200-0.22926000H0.687867002.02487700-0.37326400Zero-pointcorrection=0.170160(Hartree/Particle)ThermalcorrectiontoEnergy=0.181314ThermalcorrectiontoEnthalpy=0.182258ThermalcorrectiontoGibbsFreeEnergy=0.131364Sumofelectronicandzero-pointEnergies=-462.342848SumofelectronicandthermalEnergies=-462.331693SumofelectronicandthermalEnthalpies=-462.330749SumofelectronicandthermalFreeEnergies=-462.381643

16

Np+-Ar

C0.85924900-2.379489000.69295600C0.79758500-1.170349001.39629500C0.732435000.058356000.71318900C0.732435000.05835600-0.71318900C0.79758500-1.17034900-1.39629500C0.85924900-2.37948900-0.69295600H0.651261001.293299002.47838700H0.90671100-3.312222001.23656400H0.79606400-1.177644002.47836300C0.653262001.286218001.39631100C0.653262001.28621800-1.39631100H0.79606400-1.17764400-2.47836300H0.90671100-3.31222200-1.23656400C0.572400002.49428600-0.69297200C0.572400002.494286000.69297200H0.651261001.29329900-2.47838700H0.509395003.42610300-1.23658900H0.509395003.426103001.23658900Ar-2.72811300-0.218185000.00000000Zero-pointcorrection=0.147202(Hartree/Particle)ThermalcorrectiontoEnergy=0.156845ThermalcorrectiontoEnthalpy=0.157789ThermalcorrectiontoGibbsFreeEnergy=0.107375Sumofelectronicandzero-pointEnergies=-913.166828SumofelectronicandthermalEnergies=-913.157185SumofelectronicandthermalEnthalpies=-913.156241SumofelectronicandthermalFreeEnergies=-913.206655

17

Bz+

C0.000000000.000000001.37831500C0.000000001.244689000.68239400C0.000000001.24468900-0.68239400C0.000000000.00000000-1.37831500C0.00000000-1.24468900-0.68239400C0.00000000-1.244689000.68239400H0.000000000.000000002.46089000H0.000000002.167320001.24492700H0.000000002.16732000-1.24492700H0.000000000.00000000-2.46089000H0.00000000-2.16732000-1.24492700H0.00000000-2.167320001.24492700Zero-pointcorrection=0.097446(Hartree/Particle)ThermalcorrectiontoEnergy=0.102679ThermalcorrectiontoEnthalpy=0.103624ThermalcorrectiontoGibbsFreeEnergy=0.069959Sumofelectronicandzero-pointEnergies=-231.907949SumofelectronicandthermalEnergies=-231.902716SumofelectronicandthermalEnthalpies=-231.901771SumofelectronicandthermalFreeEnergies=-231.935436Bz+-Ar

C-0.956115001.963583000.00000000C-0.956647001.268847001.24375700C-0.95664700-0.095907001.24451000C-0.95913400-0.792170000.00000000C-0.95664700-0.09590700-1.24451000C-0.956647001.26884700-1.24375700H-0.954410003.046144000.00000000H-0.956229001.831446002.16628900H-0.95455100-0.658880002.16668800H-0.96632200-1.874093000.00000000H-0.95455100-0.65888000-2.16668800H-0.956229001.83144600-2.16628900Ar2.23296200-1.367830000.00000000Zero-pointcorrection=0.098102(Hartree/Particle)ThermalcorrectiontoEnergy=0.105766ThermalcorrectiontoEnthalpy=0.106710ThermalcorrectiontoGibbsFreeEnergy=0.061731Sumofelectronicandzero-pointEnergies=-759.470343SumofelectronicandthermalEnergies=-759.462679SumofelectronicandthermalEnthalpies=-759.461735SumofelectronicandthermalFreeEnergies=-759.506714

18

Bz+-H2O(12)

C-1.39771900-0.881772000.00000000C0.00000000-0.782013000.00000000C0.658569000.504025000.00000000C-0.083817001.659943000.00000000C-1.478138001.557952000.00000000C-2.137099000.273485000.00000000H-1.87505200-1.850644000.00000000H0.63085100-1.661373000.00000000H1.739734000.509016000.00000000H0.391281002.629907000.00000000H-2.087626002.452275000.00000000H-3.218021000.244453000.00000000O3.00025900-1.577274000.00000000H3.52299400-1.847581000.76283100H3.52299400-1.84758100-0.76283100Zero-pointcorrection=0.120585(Hartree/Particle)ThermalcorrectiontoEnergy=0.129784ThermalcorrectiontoEnthalpy=0.130729ThermalcorrectiontoGibbsFreeEnergy=0.085327Sumofelectronicandzero-pointEnergies=-308.367530SumofelectronicandthermalEnergies=-308.358330SumofelectronicandthermalEnthalpies=-308.357386SumofelectronicandthermalFreeEnergies=-308.402788

19

Bz+-H2O(π)

C-0.503490001.021428001.23798200C-0.50349000-0.343829001.24129500C-0.49478800-1.045644000.00000000C-0.50349000-0.34382900-1.24129500C-0.503490001.02142800-1.23798200C-0.494963001.713993000.00000000H-0.510915001.582417002.16132400H-0.51203800-0.903141002.16561800H-0.55591300-2.123967000.00000000H-0.51203800-0.90314100-2.16561800H-0.510915001.58241700-2.16132400H-0.483233002.796081000.00000000O2.03363800-1.328793000.00000000H2.41909900-1.770797000.76701700H2.41909900-1.77079700-0.76701700Zero-pointcorrection=0.122197(Hartree/Particle)ThermalcorrectiontoEnergy=0.130826ThermalcorrectiontoEnthalpy=0.131771ThermalcorrectiontoGibbsFreeEnergy=0.087618Sumofelectronicandzero-pointEnergies=-308.366712SumofelectronicandthermalEnergies=-308.358083SumofelectronicandthermalEnthalpies=-308.357139SumofelectronicandthermalFreeEnergies=-308.401292

20

Bz-H2O(π)

C-0.613979000.71779600-1.19182200C-0.614483001.390246000.02699100C-0.611226000.671633001.21916300C-0.60906800-0.719263001.19266700C-0.60999700-1.39165700-0.02612300C-0.61169200-0.67310600-1.21827400H-0.612895001.27624200-2.11801200H-0.619373002.471917000.04778500H-0.607729001.194381002.16594600H-0.60420700-1.277687002.11886000H-0.61163200-2.47334900-0.04690900H-0.60865500-1.19582300-2.16507900O2.688217000.00530900-0.00179600H2.076308000.748607000.00058100H2.10511700-0.76066000-0.00442800

Zero-pointcorrection=0.123036(Hartree/Particle)ThermalcorrectiontoEnergy=0.130991ThermalcorrectiontoEnthalpy=0.131935ThermalcorrectiontoGibbsFreeEnergy=0.089466Sumofelectronicandzero-pointEnergies=-308.689616SumofelectronicandthermalEnergies=-308.681661SumofelectronicandthermalEnthalpies=-308.680717SumofelectronicandthermalFreeEnergies=-308.723187

21

Bz

C0.000000001.391317000.00000000C1.204916000.695658000.00000000C1.20491600-0.695658000.00000000C0.00000000-1.391317000.00000000C-1.20491600-0.695658000.00000000C-1.204916000.695658000.00000000H0.000000002.473143000.00000000H2.141804001.236571000.00000000H2.14180400-1.236571000.00000000H0.00000000-2.473143000.00000000H-2.14180400-1.236571000.00000000H-2.141804001.236571000.00000000Zero-pointcorrection=0.100359(Hartree/Particle)ThermalcorrectiontoEnergy=0.104742ThermalcorrectiontoEnthalpy=0.105687ThermalcorrectiontoGibbsFreeEnergy=0.075253Sumofelectronicandzero-pointEnergies=-232.240297SumofelectronicandthermalEnergies=-232.235913SumofelectronicandthermalEnthalpies=-232.234969SumofelectronicandthermalFreeEnergies=-232.265403