Calculation of the Microscopic and Macroscopic Linear and Nonlinear Optical Properties of Acetonitrile:  I. Accurate Molecular Properties in the Gas Phase and Susceptibilities of the Liquid in Onsager's Reaction-Field Model

Reis, Heribert; Παπαδόπουλος, Μάνθος Γ.; Avramopoulos, Aggelos

doi:10.1021/jp0222346

Cited by 29 publications

(30 citation statements)

References 59 publications

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“…As for water, we find that predictions relying on MP2 electronic structure calculations are in fairly good agreement with the results based on CCSD͑T͒. However, as is well known, 45,46 Hartree-Fock is not a reliable method to calculate PV polarizabilities. For formaldehyde using potentials and property surfaces derived on the basis of Hartree-Fock calculations leads to a PV isotropic polarizability which is ϳ50% higher in magnitude than our CCSD͑T͒ ␣ nr predictions.…”

Section: Convergence With Respect To Details Of the Potential And Prosupporting

confidence: 77%

Linear response functions for a vibrational configuration interaction state

Christiansen¹,

Kongsted²,

Paterson

et al. 2006

The Journal of Chemical Physics

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Linear response functions are implemented for a vibrational configuration interaction state allowing accurate analytical calculations of pure vibrational contributions to dynamical polarizabilities. Sample calculations are presented for the pure vibrational contributions to the polarizabilities of water and formaldehyde. We discuss the convergence of the results with respect to various details of the vibrational wave function description as well as the potential and property surfaces. We also analyze the frequency dependence of the linear response function and the effect of accounting phenomenologically for the finite lifetime of the excited vibrational states. Finally, we compare the analytical response approach to a sum-over-states approach.

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Section: Convergence With Respect To Details Of the Potential And Prosupporting

confidence: 77%

Linear response functions for a vibrational configuration interaction state

Christiansen¹,

Kongsted²,

Paterson

et al. 2006

The Journal of Chemical Physics

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“…Including γ increases the ion-induced intensity I i VH,∞ for acetonitrile by the factor [1 + 3k B T γ ⊥ /(µ β ⊥ )] 2 = 1.23, calculated using the ab initio results µ = 4.59 D, β | | = 67.7 au, and γ | | = 4776 au for liquid phase ESHG at λ = 1064 nm. 43 Including orientation correlations increases I VH,0 by a factor C T = 1.4, and including collision-induced HRS increases I VH,0 by a further factor 1/0.70. The revised estimate is then B = 1.35, which is still 1.5× larger than the experimental value for acetonitrile.…”

Section: Ion-induced Hrsmentioning

confidence: 98%

“…44, 514.5 nm, MCSCF RAS) or 3.0 (Ref. 43, 1064 nm, CCSD(T), d-aug-cc-pVDZ), and recent QM/Monte Carlo calculations for nitrobenzene solutions indicate further small changes in β when nearest neighbour orientation correlations are explicitly included. 45 The intermolecular interactions produce both orientation correlation and molecular distortion.…”

Section: Coherent Hrs From Dipole Orientation Correlationmentioning

confidence: 99%

What is measured by hyper-Rayleigh scattering from a liquid?

Rodriquez

Shelton

2018

The Journal of Chemical Physics

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Polarization and angle dependence of hyper-Rayleigh scattering (HRS) measured for liquid acetonitrile and dimethyl sulfoxide (DMSO) is analyzed in terms of contributions from randomly oriented molecules and additional contributions produced during intermolecular collisions and induced by the electric field of dissolved ions. All three contributions show the effect of long-range correlation, and the correlation functions are determined using the HRS observations combined with the results of molecular dynamics simulations. HRS from acetonitrile is polarized transverse to the scattering vector. This is due to long-range molecular orientation correlation produced by the dipole-dipole interaction, and correlation at distances r > 100 nm must be included to account for the HRS observations. Analysis of the HRS measurements for acetonitrile determines the length scale a = 0.185 nm for the long-range longitudinal and transverse orientation correlation functions B=-2B=a/r. Transverse polarized collision-induced HRS is also observed for acetonitrile, indicating long-range correlation of intermolecular modes. Strong longitudinal HRS is induced by the radial electric field of dissolved ions in acetonitrile. For DMSO, the angle between the molecular dipole and the vector part of the first hyperpolarizability tensor is about 100°. As a result, HRS from the randomly oriented molecules in DMSO is nearly unaffected by dipole correlation, and ion-induced HRS is weak. The strong longitudinal polarized HRS observed for DMSO is due to the collision-induced contribution, indicating long-range correlation of intermolecular modes. The HRS observations require correlation that has r long-range asymptotic form, for molecular orientation and for intermolecular vibration and libration, for both acetonitrile and DMSO.

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“…Molecular NLO properties in the condensed phase can significantly differ from those observed for isolated chromophores. ,,,− Theoretical models aiming at accounting for the condensed-phase effects in solutions are commonly split into two main categories. Implicit solvation models describe the solvent as a homogeneous medium with a cavity containing the solute molecule.…”

Section: Introductionmentioning

confidence: 99%

Accurate Nonlinear Optical Properties of Solvated para-Nitroaniline Predicted by an Electrostatic Discrete Local Field Approach

et al. 2020

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A general computational protocol for accurate predictions of nonlinear optical (NLO) properties of solvated molecules based on the rigorous local field (RLF) approach taking all relevant effects into account is presented. para-Nitroaniline (pNA) was taken as a model NLO system dissolved in cyclohexane, tetrahydrofuran, and 1,4-dioxane. Molecular dynamics (MD) simulations employing either non-polarizable or polarizable force fields were used to generate representative sets of structures of the solutions. The static NLO properties of the solute were calculated at the MP2/aug-cc-pVDZ level of theory with the multiplicative scaling method used to account for the frequency dispersion of the properties. Focusing on the electric field-induced second harmonic generation (EFISH) and hyper-Rayleigh scattering (HRS), a good agreement between calculated results and experimental measurements was achieved with a polarizable force field. While the solvent effects on the vibrational contributions to the static molecular properties are significant, they remain small for both EFISH and HRS. Our results show that the proposed approach yields reliable predictions of dynamic NLO properties of solvated chromophores, which paves a route to further applications of the RLF approach to study a wide range of NLO phenomena in heterogeneous environments.

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Calculation of the Microscopic and Macroscopic Linear and Nonlinear Optical Properties of Acetonitrile: I. Accurate Molecular Properties in the Gas Phase and Susceptibilities of the Liquid in Onsager's Reaction-Field Model

Cited by 29 publications

References 59 publications

Linear response functions for a vibrational configuration interaction state

Linear response functions for a vibrational configuration interaction state

What is measured by hyper-Rayleigh scattering from a liquid?

Accurate Nonlinear Optical Properties of Solvated para-Nitroaniline Predicted by an Electrostatic Discrete Local Field Approach

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