geometry optimization
DESCRIPTION
DFT Study of Hyperfine Interactions in Some Types of the Complexes Oleg Poleshchuk, Natalya Khramova, Alexander Fateev Tomsk State Pedagogical University, Russia. Geometry optimization. Bond Lengths. - PowerPoint PPT PresentationTRANSCRIPT
1
DFT Study of Hyperfine DFT Study of Hyperfine Interactions in Some Types of Interactions in Some Types of
the Complexesthe ComplexesOleg Poleshchuk, Natalya Khramova,
Alexander FateevTomsk State Pedagogical University,
Russia
2
Geometry optimizationGeometry optimizationSO3-B complexes
B3PW91/6-311+G(df,pd)BP86/TZ2P+ in ADF
XY-B complexes
BHandHLYP/aug-cc-pVTZ 3-21G*,DGDZVP (iodine)BP86E/TZ2P+(ZORA) in ADF
MHal-B complexes
B3LYP/SDD, B3LYP/DGDZVP BP86/TZ2P+(ZORA) in ADF
3
Bond LengthsBond Lengths Complex RD-A, Å Complex RD-A, Å
Exp. Cal. Exp. Cal.HCN.SO3 2.577 2.538 ICl.CO 3.011 2.960H3N.SO3 1.957 2.053 ICl.NH3 2.711 2.600Py.SO3 1.915 1.983 ICl.Py 2.290 2.519(CH3)3N.SO3 1.912 1.997 I2
.Py 2.310 2.644Cl2
.NH3 2.730 2.685 AuCl.CO 2.217 2.259SbCl5
.OPMe3 1.94 2.11 AuCl.Ar 2.198 2.261SnCl4
.(OSMe2)2 2.11 2.24 AgBr.CO 2.373 2.400TiCl4
. (CH3CN)2 2.21 2.28 AgBr.Ar 2.393 2.427TiCl4
. (OPCl3)2 2.22 2.20 CuF.CO 1.736 1.758ICl.Ar 3.576 3.761 CuBr.CO 2.182 2.225
4
• A comparison of the geometrical para-meters calculated by us with the experimental data of free molecules and complexes displays that the bond lengths have been overestimated.
• Analysis leads to the following corre-lations between the calculated and experimental bond lengths and valence angles for the compounds studied.
5
SOSO33-В-В complexes complexes
1,9 2,0 2,1 2,2 2,3 2,4 2,5 2,6 2,71,9
2,0
2,1
2,2
2,3
2,4
2,5
2,6SO3HCN
SO3HCCCN
SO3(HCN)2
SO3MeCN
(HCN)2
(HCN)3
SO3PySO3NMe3
SO3NH3
Calc
ulat
ed b
ond
leng
th, А
Experimental bond length, А
R(cal.) = 0.46 + 0.79 R(exp.) (r=0.991; s=0.03; n=9)
Correlation between experimental and calculated at B3PW91/6-311+G(df,pd) level bond lengths.
92 94 96 98 100
92
93
94
95
96
97
98
99
SO3NMe3
SO3Py
SO3NH3
SO3(HCN)2
SO3MeNSO3HCN
SO3HCCCNCalc
ulat
ed d
egre
e NS
O,
0
Experimental degree NSO, 0
NSO(cal.) = 23.3 + 0.75 NSO(exp.) (r=0.999; s=0.16; n=7)
Correlation between experimental and calculated at B3PW91/6-311+G(df,pd) level valence degree.
6
Dependence between experimental and calculated at BHandHLYP/aug-cc-pVTZ level bond lengths.
XYXY--B complexesB complexes
1,6 1,8 2,0 2,2 2,4 2,6 2,8 3,0 3,2
1,6
1,8
2,0
2,2
2,4
2,6
2,8
3,0
3,2
Rcal. = 0,13 + 0,94 Rexp. (r=0,994; s=0,04; n=21)
Calc
ulat
ed b
ond
leng
th, А
Experimental bond length, А
7
HalM-L complexesHalM-L complexes
1,6 1,8 2,0 2,2 2,4 2,6 2,8 3,01,6
1,8
2,0
2,2
2,4
2,6
2,8
3,0
Rcal.=0.13+0.92Rexp. (r=0.999; s=0.01; n=27)
Calc
ulat
ed b
ond
leng
th,A
Experimental bond length,A
Dependence between experimental andcalculated at B3LYP/dgdzvp level bondlength in Au,Ag,Cu complexes
8
HalM-L complexes
2,10 2,15 2,20 2,25 2,30 2,35 2,40 2,45 2,50 2,552,05
2,10
2,15
2,20
2,25
2,30
2,35
2,40
2,45
Rcal.=0.2+0.89Rexp. (r=0.982; s=0.02; n=22)
Calc
ulat
ed b
ond
leng
th,A
Experimental bond length,A
Correlation between the calculated atB3LYP/DGDZVP and experimental bond lengthsfor the Nb, Sb and Ta compounds
9
Rotational constantsRotational constantsComplex В0, MHz Complex В0, MHz
Exp. Cal. Exp. Cal.
H3N.SO3 4378 4189 ClF.CH3CN 919 919
(CH3)3N.SO3 1633 1585 ICl.CO 903 888
HCN.SO3 409 445 ICl.NH3 1608 1604
CH3CN.SO3 1016 1038 AuCl 3519 3306
HCCCN.SO3 655 665 AuClCO 1404 1367
(HCN)2.SO3 409 419 CuClCO 1563 1527
Cl2.NH3 1895 1890 CuBrCO 1034 1011
ClF.NH3 3316 3328 AgClCO 1316 1299
BrCl.NH3 1801 1815 AgBrCO 852 840B0(cal.) =-38 + 1.05 B0(exp.) (r=0.9999; s=14; n=7)
for SO3 complexes
B0(cal.) = 10.7 + 0.99 B0(exp.) (r=0.9999; s=34; n=22) for halogen complexes
В0(cal.) = 15.1 + 0,95 В0(exp.) (r = 0.998; s = 49; n = 13) for metal complexes
10
0 200 400 600 800 1000 1200 14000
200
400
600
800
1000
1200
1400
(cal.)=9+1.04(exp.) r=0.999;s=20;n=24
Calc
ulat
ed fr
eque
ncy,
cm-1
Experimental frequency,cm-1
Correlation between experimental and calculated at B3LYP/dgdzvp level IR-frequencies in SO3and halogen complexes
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• The halogen, metal and nitrogen nuclear quadrupole coupling constants obtained by these calculations substantially corresponded to the data of microwave spectroscopy in the gas phase. An analysis of the quality of the calculations that employ the pseudo-potential and the expanded basis set for the halogen compounds was carried out. The ZORA model is
• shown to be a viable alternative to the computa-• tionally demanding pseudo-potential model for
the calculation of the iodine and metal (Nb, Au, Sb) quadrupole coupling constants in molecules.
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NQCC NQCC 1414N inN in SOSO33 complexes complexes
0
1
2
3
4
5
HCN HCCCN СН3CN H3N Py (CH3)3N
Bases
NQ
CC
N, M
Hz
Exp.GaussADF
NQCC nitrogen changing by complex formation
0
1
2
3
4
5
HCN HCCCN СН3CN H3N Py (CH3)3N
NQCC
N b
ase
min
us c
ompl
ex
Exp.
Gauss
ADF
-6 -5 -4 -3 -2 -1
-6
-5
-4
-3
-2
-1
NH3
MeCNHCCCN
(HCN)2Py
NMe3
SO3HCN
(HCN)3
SO3(HCN)2
SO3HCCCN
SO3MeCN
SO3NH3
SO3NMe3
SO3Py
e2 Qq zz
-14N(
cal.)
,MHz
e2Qqzz-14N(exp.),MHz
Correlation between experimental and calculated at B3PW91/6-311+G(df,pd) level 14N-NQCC in SO3 complexes.
e2QqzzN(cal.) =-0.09 + 1.05e2Qqzz
N(exp.) (r=0.989; s=0.2; n=18)
e2QqzzN (cal.) =-0.05 + 0.96 e2Qqzz
N (exp.)
(r = 0.970; s = 0.3; n = 11)from ADF calculations
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1414N-NQCC in nitrogen moleculesN-NQCC in nitrogen molecules
Dependence between experimental and calculated at BP86/TZ2P+ level NQCC values of N nuclei in nitrogen molecules
e2Qq(exp.) = -0.3 + 0.94 e2Qq (cal.)
(r = 0.997; s = 0.2; n = 27)
-8 -6 -4 -2 0 2 4 6-8
-6
-4
-2
0
2
4
6
Expe
rimen
tal 14
N- N
QCC
,MHz
Calculated 14N- NQCC,MHz
14
1717O-NQCC in oxygen moleculesO-NQCC in oxygen molecules
Dependence between experimental and calculated at BP86/TZ2P+ level NQCC values of O nuclei in oxygen molecules
e2Qq(exp.) = 0.1 + 0.99 e2Qq (cal.)
(r = 0.997; s = 0.5; n = 17)
-10 -5 0 5 10 15-10
-5
0
5
10
15
Expe
rimen
tal 17
O- N
QCC
,MHz
Calculated 17O- NQCC,MHz
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NQCC in XY-B complexesNQCC in XY-B complexes
Dependence between experimental and calculated at BHandHLYP/aug-cc-pVTZ level NQCC values of Cl, Br, N nuclei in XY-B complexes
e2Qq(cal.) = 0.7 + 1.005 e2Qq (exp.)
(r = 0.9999; s = 3.4; n = 35)
-200 0 200 400 600 800 1000
-200
0
200
400
600
800
1000
Calc
ulat
ed 14
N- N
QCC
,MHz
Experimental 14N- NQCC,MHz
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-3000 -2500 -2000 -1500 -1000
-3600
-3400
-3200
-3000
-2800
-2600
-2400
-2200
NQCC(cal.)=-1475+0.65NQCC(exp.)r=0.961;s=125;n=12
e2 Qq zz
(cal
.) M
Hz
e2Qqzz (exp.) MHz
Dependence between calculated and experimental 127I-NQCC values of the XY...B(XY=I) complexes at B3LYP/dgdzvp level
NQCC iodine nucleiNQCC iodine nuclei
Dependence between calculated and experimental 127I-NQCC values of the XY...B(XY=I) complexes at ZORA in ADF
-3200 -3000 -2800 -2600 -2400 -2200 -2000 -1800
-3000
-2500
-2000
-1500
-1000
NQCC(cal.)=1600+1.6NQCC(exp.)r=0.992;s=75;n=17
e2 Qqz
z (c
al.)
MHz
e2Qqzz (exp.) MHz
17
3535Cl- NQCC in XY-B complexesCl- NQCC in XY-B complexes
Dependence between experimental and calculated at BP86/TZ2P+ level NQCC values of Cl and Br nuclei in XY-B complexes
e2Qq(exp.) = -5.1 + 1.05 e2Qq (cal.)
(r = 0.997; s = 3.5; n = 48)
0 50 100 150 200
0
50
100
150
200
250
n35Cl
,79Br
(exp
.),M
Hz
n35Cl,79Br(cal.),MHz
18
50 100 150 200 250 300 350 400 450 500
50
100
150
200
250
300
350
400
450
QCC Sb(exp)=-13+0.9QCC Sb(cal.)r=0.994;s=11;n=11
e2 Qq zz
121 Sb
(exp
.),M
Hz
e2Qqzz121Sb(cal.),MHz
Calculated at B3LYP/dgdzvp versusexperimental 121Sb compounds
19
40 60 80 100 120 140 160 180 200100
150
200
250
300
350
400
QCC Sb(exp)=35+1.8QCC Sb(cal.)r=0.992;s=10;n=13
e2 Qq zz
121 Sb
(cal
.),M
Hz
e2Qqzz121Sb(exp.),MHz
Calculated at BP86/TZ2P+(ZORA) versusexperimental 121Sb compounds
20
60 80 100 120 14020
40
60
80
100
120
QCC Nb(exp)=-44+1.1QCC Nb(cal.)r=0.993;s=4;n=6
e2 Qq zz
93Nb
(exp
.),M
Hz
e2Qqzz93Nb(cal.),MHz
Calculated at B3LYP/dgdzvp versusexperimental 93Nb compounds
21
-1000 -500 0 500 1000 1500 2000
-1000
-500
0
500
1000
1500
2000
QCC Nb,Ta(exp)=2.9+1.01QCC Nb,Ta(cal.)r=0.9999;s=13;n=14
e2 Qq zz
93Nb
,181 Ta
(cal
.),M
Hz
e2Qqzz93Nb,181Ta(exp.),MHz
Calculated at BP86/TZ2P+(ZORA) versusexperimental 93Nb and 181Ta compounds
22
-1200 -1000 -800 -600 -400 -200 0 200-700
-600
-500
-400
-300
-200
-100
0
QCC Au(cal.)=2.9+1.01QCC Au(exp.)r=0.992;s=30;n=12
e2 Qq zz
197 Au
(cal
.),M
Hz
e2Qqzz197Au (exp.),MHz
Calculated at BP86/TZ2P+(ZORA) versusexperimental 197Au compounds
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NQCC in Xe-B complexesNQCC in Xe-B complexes
Dependence between experimental and calculated at B3LYP/DGDZVP level NQCC values of Xe nuclei in Xe-B complexes
e2Qq(exp.) = -0.3 + 0.9 e2Qq (cal.)
(r = 0.987; s = 0.8; n = 6)
-10 -8 -6 -4 -2 0 2 4 6-10
-8
-6
-4
-2
0
2
4
6
Calculated 131Xe- NQCC,MHz
Expe
rimen
tal 13
1 Xe- N
QCC
,MHz
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Energy decomposition analysis (kcal/mol)Energy decomposition analysis (kcal/mol) Complex Eprep. EPauli Eelectr. Eorb. De
ADF/D0gauss
HCN.SO3 0.86 22.44 -13.25 -10.57 0.5/4.2
HCCCN.SO3 0.94 23.4 -13.57 -11.13 0.4/3.5
(HCN)2.SO3 0.67 31.42 -18.79 -16.08 2.8/7.0
СН3CN.SO3 1.72 35.15 -21.05 -18.22 2.4/7.8
H3N.SO3 6.51 125.26 -76.37 -71.53 16.1/18.4
Py.SO3 9.98 153.33 -90.53 -89.73 17.0/23.1
(СН3)3N.SO3 11.55 162.94 -97.37 -97.49 20.4/28.7
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• The Eelstat. term in all complexes is close to the Eorb term, although for weakly bound complexes the electrostatic interactions tend to be slightly larger than the covalent ones.
• The calculated values of the bonding energy in these complexes using the ADF package differ from those obtained at the B3PW91/6-311+G(df,pd) level. However, the variation from one system to another is similar:
• DeADF = -4.5 + 0.83 D06-311+G(df,pd) (r=0.990; s=1.4; n=7)
26
NBO analysis for SONBO analysis for SO33 complexes complexesComplex Orbital Occupaid Hybridization of S
atom (%)Eij
(2) (kcal/ mol)
Interaction between bonding and anti-bonding orbitalss p d
HCN.SO3 LP(N) 1.942 33.1 65.3 1.6 8.1 LP(N)BD*(S-O)
HCCCN.SO3 LP(N) 1.937 32.1 66.3 1.6 8.6 LP(N)BD*(S-O)
(HCN)2.SO3 LP(N) 1.920 31.2 67.0 1.8 13.1 LP(N)BD*(S-O)
СН3CN.SO3 LP(N) 1.906 33.0 65.3 1.7 15.4 LP(N)BD*(S-O)
H3N.SO3 BD(N-S) 1.888 17.7 43.5 38.8 93.1 BD(N-S)BD*(S-O)
Py.SO3 BD(N-S) 1.851 16.4 46.8 36.8 105.4 BD(N-S)BD*(S-O)
(СН3)3N.SO3 LP(O) 1.751 12.5 85.1 2.4 142.8 LP(O)BD*(N-S)
27
SO3…B complexes
• NBO second-order interaction energies of n-complexes shown that the LP(N) → π*SO3 (LP=lone electron pair) donor-acceptor interaction is the source of such intermolecular charge transfer.
• DeADF/kcal/mol = 5.4 + 0.2 Eij(2)/kcal/mol (r=0.998; s=0.7; n=7)
28
0,00 0,05 0,10 0,15 0,20 0,25 0,30 0,350
5
10
15
20
25
30SO3NMe3
SO3Py
SO3NH3
SO3MeCN
SO3(HCN)2
SO3HCCCN
SO3HCN
D 0, kc
al/m
ol
charge transfer q(B--->X),eBonding energy versus charge transfer (NAO) for SO3 complexes
D0 = 2.3 + 70.4 q(r=0.985; s=1.9; n=7)
29
Bonding energy by ADF is close to outcomes at the BHandHLYP/aug-cc-pVTZ De
ADF =-0.1 + 0.9 Deaug-cc-pVTZ (r=0.995; s=0.5; n=7)
Complex Eprep. EPauli Eelectr. Eorb. De RB-Ycal. Eij
(2)
IClAr 0.0 0.1 0.0 -0.2 0.1 4.433 1.0
IClCO 0.7 67.8 -34.3 -36.5 2.3 2.413 13.5
I2Py 0.4 48.6 -32.1 -25.6 8.7 2.564 36.4
IBrPy 1.7 44.9 -31.3 -24.9 9.6 2.576 45.2
I2N(СН3)3 1.8 50.0 -33.2 -28.4 9.7 2.601 40.2
IClNH3 1.3 45.2 -32.6 -24.1 10.1 2.576 53.5
IClPy 1.9 59.4 -40.9 -31.5 11.1 2.475 56.8
Energy decomposition and NBO analysis (kcal/mol)Energy decomposition and NBO analysis (kcal/mol)
30
ICl…B complexes• The Eelstat. term in all complexes is larger than the
Eorb term. This suggests that the Y-B bonding in these complexes is more electrostatic than covalent.
• NBO second-order interaction energies of n-complexes shown that the LP(B)*XY (LP=lone electron pair, B=N, C, Ar coordinated atom) donor-acceptor interaction is the source of such intermolecular charge transfer.
• DeADF/kcal/mol = 0.2 + 0.2 Eij
(2)/kcal/mol (r=0.978; s=1.0; n=7)
31
-0,02 0,00 0,02 0,04 0,06 0,08 0,10 0,12 0,14 0,16-2
0
2
4
6
8
10
12
14
De= 0,01 + 78,8 q (r=0,980; s=0,9; n=26)
D e, kc
al/m
ol
charge transfer q(B--->X),e
Dependence between De and electron transfer (NAO) in XY...B complexes
32
• The calculated bonding energies for both complexes are strongly correlated with the extent of electron transfer from base to the acceptor from the natural atomic charges.
• These correlations contrasts with the different situation found for the main group and transition metal complexes.
• Apparently, related to this is the observation that, according to our calculations, the electronic charge changes are significant only on the two atoms immediately involved in the intermolecular bond, while in metal chloride complexes such changes are appreciable on all atoms.
33
Complex ΔЕprep. ΔЕPauli ΔЕelectr. ΔЕorb. DeADF De
Gauss ΔЕij(2)
OC-CuCl 0.0 96.0 -80.5 -56.7 41.2 36.0 110
OC-AgCl -0.1 99.7 -77.6 -44.5 22.5 24.6 103
OC-AuCl -0.2 176.9 -139.4 -86.0 48.7 46.4 256
Py-CuCl 0.7 77.4 -80.5 -33.9 36.3 38.3 66
Py-AgCl 0.4 68.7 -66.2 -24.7 21.8 27.5 56
Py-AuCl 0.7 111.1 -102.6 -46.5 37.3 40.7 119
(СН3)3PO-CuCl 1.7 60.3 -63.6 -28.6 30.2 36.2 79
(СН3)3PO-AgCl 1.0 49.6 -49.5 -20.2 19.1 26.0 23
(СН3)3PO-AuCl 1.9 72.8 -67.4 -34.6 27.3 33.6 58
Energy decomposition analysis,kcal/molEnergy decomposition analysis,kcal/mol
34
Decomposition of the formation energy of the complexes by ADF, kcal/mol
Complex Eprep EPauli Eelstat Eorbtot Eint De/D0Gauss
SbCl5SMe2 7.9 83.2 -54.3 -48.9 -20.0 12.1/13.5
SbCl5OPMe3 11.1 128.0 -94.0 -65.7 -31.7 20.6/25.4
SbCl5NCCH3 4.8 72.4 -49.1 -34.1 -10.8 6.0/9.9
SbCl5OPCl3 4.1 46.2 -30.7 -20.9 -5.4 1.3/5.3
SbCl5OSCl2 2.2 15.7 -10.0 -6.2 -0.5 1.7/0.7
SbCl5Py 9.4 109.3 -79.6 -56.6 -26.9 17.5/20.0
35
0 5 10 15 20 25 30-5
0
5
10
15
20
25
30
35
40
-DH=-4.1+1.5Der=0.974;s=2.7;n=11
-DH(
exp.
),kca
l/mol
De(cal.),kcal
Calculated bonding energy at PB86/TZ2P+(ZORA) versusexperimental enthalpy values for Sb complexes
36
MCln…B complexes
• The Eelstat. term in all complexes is larger than the Eorb term. This suggests that the M-B bonding in these complexes is more electrostatic than covalent.
• NBO second-order interaction energies of nv-complexes shown that the LP(B)*MCl (LP=lone electron pair, B=N, O, S, P coordinated atom) donor-acceptor interaction is the source of such intermolecular charge transfer.
• DeADF/kcal/mol = 19.6 + 0.12 Eij
(2)/kcal/mol (r=0.80; s=6.0; n=12)
37
Conclusions• The calculations clearly show that the calculated by
Gaussian and ADF bond lengths, IR-spectra correlate with the experimental values.
• The halogen, nitrogen and metal NQCC’s obtained by both calculations substantially corresponded to the data of microwave and NQR-spectroscopy.
• The calculated by both methods stabilization energies are close to the experimental values.
• We have found the correlations between charge donation and the calculated bonding energies of the halogen and SO3 complexes contrasts with the different situation found for the main group and transition metal complexes.
• From EPA scheme follows that for all complexes the electrostatic bonding is a little bit more than covalent bonding.