Theoretical investigation of intramolecular vibrational energy redistribution in HFCO and DFCO induced by an external field.

The present paper is devoted to a full quantum mechanical study of the intramolecular vibrational energy redistribution in HFCO and DFCO. In contrast to our previous studies [Pasin et al., J. Chem. Phys. 124, 194304 (2006) and 126, 024302 (2007)], the dynamics is now performed in the presence of an external time-dependent field. This more closely reflects the experimental conditions. A six-dimensional dipole surface is computed. The multiconfiguration time-dependent Hartree method is exploited to propagate the corresponding six-dimensional wave packets. Special emphasis is placed on the excitation of the out-of-plane bending vibration and on the dissociation of the molecule. In the case of DFCO, we predict that it is possible to excite the out-of-plane bending mode of vibration and to drive the dissociation to DF+CO with only one laser pulse with a fixed frequency and without excitation of an electronic state.

Computation of vibrational energy levels and eigenstates of fluoroform using the multiconfiguration time-dependent Hartree method.

A theoretical study of the vibrational spectrum of the CHF(3) molecule is carried out with the aid of the multiconfiguration time-dependent Hartree (MCTDH) algorithm. In order to obtain the eigenvalues and the eigenstates, recent developments in the MCTDH improved relaxation method in a block form are exploited. Around 80 eigenvalues are reported, which are converged with a very high accuracy. The results obtained with our study are compared with those of a previous work using the wave operator sorting algorithm approach. The present investigation exemplifies the robustness and the accuracy of the improved relaxation method.

Variational calculation of specific, highly excited vibrational states in DFCO: comparison with experimental data.

A stimulated emission pumping spectra of jet-cooled DFCO performed by Crane et al. (J. Mol. Spectrosc. 1997, 183, 273) has provided a great number of ro-vibrational lines up to 9000 cm(-1) of excitation energy. By combining a Jacobi-Wilson (JW) approach with a Davidson scheme, we calculate the lines provided by the experiment up to 9000 cm(-1) using an ab initio global potential energy surface (PES) developed by Kato et al. (J. Chem. Phys. 1997, 107, 6114). Comparisons between experimental and calculated data provide a critical test of the quality of the PES used. We show that the variational calculated energies can be efficiently corrected by taking into account the error observed for the A' fundamental transitions nu(i) (i = 1, ..., 5) and the first overtone 2nu(6). A detailed analysis of the eigenstates obtained by the calculation allows one to quantify the coupling between the different modes. Such an information is essential to understand and predict the energy flow through a DFCO molecule that is initially excited.

Theoretical investigation of highly excited vibrational states in DFCO: calculation of the out-of-plane bending states and simulation of the intramolecular vibrational energy redistribution.

A previously developed modified Davidson scheme [C. Iung and F. Ribeiro, J. Chem. Phys. 121, 174105 (2005)] is applied to compute and analyze highly excited (nu2,nu6) eigenstates in DFCO. The present paper is also devoted to the simulations of the intramolecular vibrational energy redistribution (IVR) initiated by an excitation of the out-of-plane bending vibration (nnu6, n=2,4,6, . . . ,18, and 20). The multiconfiguration time-dependent Hartree method is exploited to propagate the corresponding six-dimensional wave packets. A comprehensive comparison with experimental data as well as with previous simulations of IVR in HFCO [G. Pasin et al. J. Chem. Phys. 124, 194304 (2006)] is presented.

Comparison of perturbative and variational treatments of molecular vibrations: application to the vibrational spectrum of HFCO up to 8000 cm(-1).

We calculated highly excited states of the HFCO molecule, comparing results from two methods. In the first method, Van Vleck perturbation theory is used to transform away all off-diagonal couplings except those between nearly degenerate states. This perturbative transformation leads to a matrix representation where eigenvalues are obtained with relatively small matrices. In the second method, variational eigenvalues are obtained by combining the Jacobi-Wilson approach with the block-Davidson scheme. The key ingredient here is a prediagonalized-perturbative scheme applied to a subspace of a curvilinear normal-mode basis set. Comparisons of the two methods provide a critical test of the less time-consuming perturbation theory. Two different coordinate sets are used to test the sensitivity of the results to coordinate choice. Perturbation theory also requires a polynomial fit to the potential. The implications of this restriction are investigated.

Theoretical investigation of intramolecular vibrational energy redistribution in highly excited HFCO.

The present paper is devoted to the simulations of the intramolecular vibrational energy redistribution (IVR) in HFCO initiated by an excitation of the out-of-plane bending vibration [nnu(6)=2,4,6,...,18,20]. Using a full six-dimensional ab initio potential energy, the multiconfiguration time-dependent Hartree (MCTDH) method was exploited to propagate the corresponding six-dimensional wave packets. This study emphasizes the stability of highly excited states of the out-of-plane bending mode which exist even above the dissociation threshold. More strikingly, the structure of the IVR during the first step of the dynamics is very stable for initial excitations ranging from 2nu(6) to 20nu(6). This latter result is consistent with the analysis of the eigenstates obtained, up to 10nu(6), with the aid of the Davidson algorithm in a foregoing paper [Iung and Ribeiro, J. Chem. Phys. 121, 174105 (2005)]. The present study can be considered as complementary to this previous investigation. This paper also shows how MCTDH can be used to predict the dynamical behavior of a strongly excited system and to determine the energies of the corresponding highly excited states.

Calculation of specific, highly excited vibrational states based on a Davidson scheme: application to HFCO.

We present the efficiency of a new modified Davidson scheme which yields selectively one high-energy vibrationally excited eigenstate or a series of eigenstates. The calculation of a highly vibrationally excited state psi located in a dense part of the spectrum requires a specific prediagonalization step before the Davidson scheme. It consists in building a small active space P containing the zero-order states which are coupled with the zero-order description of the eigenstate of interest. We propose a general way to define this active space P which plays a crucial role in the method. The efficiency of the method is illustrated by computing and analyzing the high-energy excited overtones of the out-of-plane mode [formula: see text] in HFCO. These overtone energies correspond to the 234th, 713th, and 1774th energy levels in our reference basis set which contains roughly 140,000 states. One of the main advantages of this Davidson scheme comes from the fact that the eigenstate and eigenvalue convergence can be assessed during the iterations by looking at the residual [formula: see text]. The maximum value epsilon allowed for this residual constitutes a very sensitive and efficient parameter which sets the accuracy of the eigenvalues and eigenstates, even when the studied states are highly excited and are localized in a dense part of the spectrum. The physical analysis of the eigenstates associated with the 5th, 7th, and 9th out-of-plane overtones in HFCO provides some interesting information on the energy localization in this mode and on the role played by the in-plane modes. Also, it provides some ideas on the numerical methods which should be developed in the future to tackle higher-energy excited states in polyatomics.

A Jacobi-Wilson description coupled to a block-Davidson algorithm: an efficient scheme to calculate highly excited vibrational levels.

We present a new approach based on the block-Davidson scheme which provides eigenvalues and eigenvectors of highly excited (ro) vibrational states of polyatomic molecules. The key ingredient is a prediagonalized-perturbative scheme applied to a subspace of a curvilinear normal-mode basis set. This approach is coupled to the Jacobi vector description recently developed by our group [C. Leforestier, A. Viel, F. Gatti, C. Munoz, and C. Iung, J. Chem. Phys. 114, 2099 (2001)], and applied to the HFCO and H2CO molecules, which represent the main difficulties of such calculations for any available method. The first one presents a significant state density because of its low symmetry and the presence of a fluorine atom, while strong resonances and intermode couplings occur in H2CO. This study establishes the robustness, the numerical efficiency, and the versatility of the method which is compared to the regular Lanczos and Davidson schemes. It is also shown that the eigenvectors can be obtained within a given accuracy easily set by the user. This point constitutes one of the main advantages of the method as very few potential-energy surfaces achieve an accuracy of the order of a wave number for highly excited states. Furthermore, this method allows one to restrict the calculations to selected energy levels based on their zero-order descriptions.

Intramolecular vibrational energy redistribution in the highly excited fluoroform molecule: a quantum mechanical study using the multiconfiguration time-dependent Hartree algorithm.

The present paper is devoted to a detailed study of the intramolecular vibrational energy redistribution in fluoroform initiated by a local mode excitation of the CH stretch [nnu(CH) (n=1,...,4)]. All nine internal degrees of freedom are explicitly taken into account and the full quantum mechanical simulation is performed by means of the multiconfiguration time-dependent Hartree algorithm. The existence of different time scales considerably complicates the dynamics. The mode-to-mode energy transfer is analyzed by calculating the evolution of the partial energies of all vibrational modes. This study emphasizes the crucial role played by the two-dimensional FCH bending modes which act as an energy reservoir. The fast energy flow into these bending modes significantly hinders an energy flow from the CH chromophore. Finally, our results are compared with those obtained previously with the wave operator sorting algorithm approach.