Simple finite field nuclear relaxation method for calculating vibrational contribution to degenerate four-wave mixing

A simple extended finite field nuclear relaxation procedure for calculating vibrational contributions to degenerate four-wave mixing (also known as the intensity-dependent refractive index) is presented. As a by-product one also obtains the static vibrationally averaged linear polarizability, as well as the first and second hyperpolarizability. The methodology is validated by illustrative calculations on the water molecule. Further possible extensions are suggested

Simple finite field method for calculation of static and dynamic vibrational hyperpolarizabilities: curvature contributions

In the static field limit, the vibrational hyperpolarizability consists of two contributions due to: (1) the shift in the equilibrium geometry (known as nuclear relaxation), and (2) the change in the shape of the potential energy surface (known as curvature). Simple finite field methods have previously been developed for evaluating these static field contributions and also for determining the effect of nuclear relaxation on dynamic vibrational hyperpolarizabilities in the infinite frequency approximation. In this paper the finite field approach is extended to include, within the infinite frequency approximation, the effect of curvature on the major dynamic nonlinear optical processes

Automatic generation of active coordinates for quantum dynamics calculations: application to the dynamics of benzene photochemistry

A new practical method to generate a subspace of active coordinates for quantum dynamics calculations is presented. These reduced coordinates are obtained as the normal modes of an analytical quadratic representation of the energy difference between excited and ground states within the complete active space self-consistent field method. At the Franck-Condon point, the largest negative eigenvalues of this Hessian correspond to the photoactive modes: those that reduce the energy difference and lead to the conical intersection; eigenvalues close to 0 correspond to bath modes, while modes with large positive eigenvalues are photoinactive vibrations, which increase the energy difference. The efficacy of quantum dynamics run in the subspace of the photoactive modes is illustrated with the photochemistry of benzene, where theoretical simulations are designed to assist optimal control experiments

Determination of vibrational polarizabilities and hyperpolarizabilities using field-induced coordinates

An analytical set of field-induced coordinates is defined and is used to show that the vibrational degrees of freedom required to completely describe nuclear relaxation polarizabilities and hyperpolarizabilities is reduced from 3N-6 to a relatively small number. As this number does not depend upon the size of the molecule, the process provides computational advantages. A method is provided to separate anharmonic contributions from harmonic contributions as well as effective mechanical from electrical anharmonicity. The procedures are illustrated by Hartree-Fock calculations, indicating that anharmonicity can be very important

Dynamics of hydrothermal plumes in Lake Banyoles

Aquesta tesi permet adquirir una millor comprensió de la dinàmica dels plomalls hidrotèrmics en l'estany de Banyoles i correlacionar la meteorologia amb els processos de fluïdització que s'hi produeixen. S'han trobat els patrons atmosfèrics que generen els esdeveniments de les fluïditzacions així com la seva freqüència. Això és crucial per a determinar la qualitat de l'aigua de l'estany. S'han trobat inhomogeneïtats espacials tant en el plomall crònic que es desenvolupa en la cubeta B1, com en el plomall episòdic de la cubeta B2. S'ha caracteritzat l'estructura del plomall generat a la cubeta B2 i s'ha comparat amb el desenvolupat a la cubeta B1. Finalment, s'han realitzat simulacions numèriques mitjançant un model numèric: MIT General Circulation Model, en el qual s'ha hagut de fer canvis en les condicions de contorn per a situar la font convectiva al fons de la columna d'aigua. Les simulacions s'han comparat amb els resultats experimentals trobats mitjançant campanyes.