Perturbative calculation of intermolecular interactions in orthogonalized or biorthogonal basis sets

1996 ◽  
Vol 94 (6) ◽  
pp. 333-344 ◽  
Author(s):  
P. R. Surján ◽  
C. Valley
Keyword(s):  
Intermolecular Interactions ◽  
Basis Sets ◽  
Perturbative Calculation ◽  
Biorthogonal Basis

Intermolecular Effects on Third Order Nonlinear Optical Properties

1992 ◽  
Vol 247 ◽  
Author(s):  
D. S. Dudis ◽  
A. T. Yeates ◽  
H. A. Kurtz
Keyword(s):  
Optical Properties ◽  
Intermolecular Interactions ◽  
Nonlinear Optical ◽  
Basis Set ◽  
Basis Sets ◽  
Intermolecular Potential ◽  
Correlation Effects ◽  
Third Order ◽  
Hartree Fock ◽  
Intermolecular Contacts

ABSTRACTHartree-Fock ab initio calculations have been used to examine the magnitude of non-polar intermolecular interactions on polarizabilities and second hyperpolarizabilities. In the present case two ethylene molecules were examined in a cofacial interaction. Basis set requirements and correlation effects were considered in deriving the intermolecular potential. Two basis sets were considered for the intermolecular interactions at the Hartree-Fock level, while one set of calculations was performed with corrections for correlation. It is found that intermolecular contacts at the van der Waals distance has little effect on the molecular second hyperpolarizability, but it is not clear what the effect would be for longer oligomers.

scholarly journals Water-mediated intermolecular interactions in 1,2-O-cyclohexylidene-myo-inositol: a quantitative analysis

2017 ◽  
Vol 73 (1) ◽  
pp. 20-27
Author(s):  
Gayathri Purushothaman ◽  
Kapil Juvale ◽  
Sivapriya Kirubakaran ◽  
Praveen Kumar Vemula ◽  
Vijay Thiruvenkatam
Keyword(s):  
Intermolecular Interactions ◽  
Density Functional ◽  
Crystal Packing ◽  
Inositol Phosphate ◽  
Biological Activities ◽  
Lattice Energy ◽  
Basis Sets ◽  
Water Molecules ◽  
Important Intermediate ◽  
Hydroxy Groups

The syntheses of new myo-inositol derivatives have received much attention due to their important biological activities. 1,2-O-Cyclohexylidene-myo-inositol is an important intermediate formed during the syntheses of certain myo-inositol derivatives. We report herein the crystal structure of 1,2-O-cyclohexylidene-myo-inositol dihydrate, C12H20O6·2H2O, which is an intermediate formed during the syntheses of myo-inositol phosphate derivatives, to demonstrate the participation of water molecules and hydroxy groups in the formation of several intermolecular O—H...O interactions, and to determine a low-energy conformation. The title myo-inositol derivative crystallizes with two water molecules in the asymmetric unit in the space group C2/c, with Z = 8. The water molecules facilitate the formation of an extensive O—H...O hydrogen-bonding network that assists in the formation of a dense crystal packing. Furthermore, geometrical optimization and frequency analysis was carried out using density functional theory (DFT) calculations with B3LYP hybrid functionals and 6-31G(d), 6-31G(d,p) and 6-311G(d,p) basis sets. The theoretical and experimental structures were found to be very similar, with only slight deviations. The intermolecular interactions were quantitatively analysed using Hirshfeld surface analysis and 2D (two-dimensional) fingerplot plots, and the total lattice energy was calculated.

scholarly journals Vibrational spectroscopic and Hirshfeld surface analysis of N,N'-(azanediylbis(2,1-phenylene))bis(2-chloropropanamide)

2019 ◽  
Vol 10 (4) ◽  
pp. 386-402
Author(s):  
Aysegul Suzan Polat ◽  
Ilkay Gumus ◽  
Hakan Arslan
Keyword(s):  
Surface Analysis ◽  
Intermolecular Interactions ◽  
Density Functional ◽  
Solid Phase ◽  
Hirshfeld Surface ◽  
Hirshfeld Surface Analysis ◽  
Basis Sets ◽  
Hartree Fock ◽  
Ft Ir ◽  
Ir And Raman

The title molecule, N,N'-(azanediylbis(2,1-phenylene))bis(2-chloropropanamide) (LNNN) was synthesized and characterized by means of Hirshfeld surface analysis and vibrational (FT-IR and RAMAN) studies. Ab-initio Hartree-Fock (HF) and density functional theory (DFT; BLYP, B3LYP, B3PW91 and mPW1PW91) calculations were accomplished using 6-31G(d,p) and 6-311G(d,p) basis sets. The comparison of calculated bond lengths and angles with X-ray crystal structure shows sufficient agreement. The solid phase FT-IR and FT-RAMAN spectra of LNNN have been recorded in the regions 4000-525 cm-1 and 4000-50 cm-1, respectively. A comparative analysis between the calculated and experimental vibrational frequencies was carried out and significant bands were assigned. The results indicated a good correlation between experimental and theoretical IR and RAMAN frequencies. A detailed analysis of the intermolecular interactions via Hirshfeld surface analysis and fingerprint plots revealed that supramolecular structure of the LNNN is stabilized mainly by the formation of H···H, C···H, Cl···H ve O···H  intermolecular interactions.

Intermolecular Interactions in the (CO2)2, N2-CO2 and CO-CO2 Complexes

2004 ◽  
Vol 69 (1) ◽  
pp. 177-188 ◽  
Author(s):  
Jiří Fišer ◽  
Tomáš Boublík ◽  
Rudolf Polák
Keyword(s):  
Experimental Data ◽  
Intermolecular Interactions ◽  
Basis Sets ◽  
Geometrical Parameters ◽  
Interaction Energies ◽  
Intermolecular Bond ◽  
Stable Structures ◽  
Good Agreement

Interaction energies of the most stable structures of the title complexes are calculated using the supermolecule CCSD(T) and MP4 methods and aug-cc-pVXZ (X = D, T, Q) basis sets extended by a set of midbond functions centered in the middle of the intermolecular bond. Geometrical parameters for these structures are in very good agreement with experimental data.

Some Formal Aspects of the Theory of Intermolecular Interactions and of the BSSE Problem

2008 ◽  
Vol 73 (11) ◽  
pp. 1391-1414 ◽  
Author(s):  
István Mayer
Keyword(s):  
Intermolecular Interactions ◽  
A Priori ◽  
Basis Set ◽  
Basis Sets ◽  
Intermolecular Potential ◽  
Potential Surfaces ◽  
Expectation Value ◽  
Complete Basis ◽  
Complete Basis Set ◽  
The Individual

Some results of mathematical character concerning the theory of intermolecular interactions and the BSSE problem are presented. It is shown that the concept of complete basis set may be introduced for intermolecular potential surfaces only by considering explicitly the limiting process in which the basis sets of both monomers approach completeness simultaneously. That does not lead to any overcompleteness problem if we do not postulate the existence of two complete basis sets from the outset. The intimate connection between the BSSE and the differences of some biorthogonal integrals and their "original" counterparts is also discussed. The operator of BSSE is given in terms of such differences. It is shown that in a special case, when only the overlap of the occupied orbitals is considered, the "bi-expectation" value of the energy coincides with the conventional expectation value for the single determinant wave function built up of the unperturbed orbitals of the individual monomers. It is discussed, by using a model of the biorthogonal perturbation theory, why the conceptually fully different a priori (CHA) and a posteriori (CP) schemes of BSSE correction usually give very close numerical results. (The necessary biorthogonal perturbation formalism is developed in the Appendices.) The results give justification for the additivity assumptions inherent in the CP method.

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