Angular distributions of the fragments from coulomb explosions of diatomic molecules in intense laser fields

The angular distributions of the fragments from a Coulomb explosion of a diatomic heteronuclear molecule during multielectron dissociative ionization in a superintense field are considered in terms of classical mechanics. The patterns of angular distributions of the Coulomb explosion fragments are shown to differ in different ranges of laser pulse parameters. In particular, there are two distinct modes of fragment separation: separation in a Coulomb field and separation in the field of an effective “fragment + field” potential. The effective potential includes both the force of Coulomb repulsion between the fragments and the period-averaged force exerted on the system by the field; it can be determined by using the Kramers-Henneberger method. The limits of applicability of the Kramers-Henneberger method to the problem in question are discussed. These limits specify the range of field parameters in which the fragments fly apart in a direction perpendicular to the field for the initially arbitrary orientation of the molecular axis relative to the field.     

Nuclear fusion driven by coulomb explosions of large deuterium clusters

Recent experiments on the interaction of intense, ultrafast laser pulses with large van der Waals bonded clusters have shown that these clusters can explode with substantial kinetic energy. By driving explosions in deuterium clusters with a 35 fs laser pulse, we have accelerated ions to sufficient kinetic energy to produce DD nuclear fusion. By diagnosing the fusion yield through measurements of 2.45 MeV fusion neutrons, we have found that the fusion yield from these exploding clusters varies strongly with the cluster size, consistent with acceleration of deuterons via Coulomb explosion forces.     

Gaussian expansions for polyatomic molecules

A method for obtaining finite series expansions of Slater-type atomic orbitals in terms of an arbitrary number of Gaussian-type functions is described. The method is based on numerical quadrature procedures applied to the Laplace transform of the exponential radial dependence of the Slater orbital. Accuracy of the expansions is evaluated by examining various overlap and one-electron energy integrals. A further application is made to the evaluation of two-centre Coulomb electron repulsion integrals and it is seen that six-place accuracy is obtainable using sixteen term expansions.     

Excitation of polyatomic molecules by radiation

An elementary procedure for calculating quantum mechanically the time-dependent rotation-vibration wave function for a collisionless model of a polyatomic molecule in a monochromatic radiation field is described and applied to some very simple cases. It is concluded that molecules can in principle be strongly and selectively excited at radiation intensities which are too low to produce appreciable excitation in classical calculations. The excitation process is a coherent multi-photon Rabi precession between two discrete levels followed by a transition to a quasi-continuum of vibration-rotation states.     

Renner parameters of isotopic polyatomic molecules

From a consideration of the form of the bending potential in internal coordinates for a ¹Π electronic state of a linear molecule, the equations for calculating the bending vibrational frequencies and Renner parameters of different isotopic molecules are obtained, and relations connecting the Renner parameters of different isotopes are derived. The recent results for the [Gtilde] ¹Π _u and [Htilde] ¹Π _u states of acetylene isotopes [5] are consistent with the theory, but it is not possible at present to determine the sign of ε₅₅ for the [Htilde] ¹Π _u state from the C₂HD isotope effect on ε₄₄.     

Infrared multiphoton excitation of polyatomic molecules

Results of investigations of the process of multiphoton excitation of polyatomic molecules by CO₂-laser radiation are presented. The mechanism of formation of the profiles of IR absorption bands of polyatomic molecules is discussed. New experimental methods of investigation of relaxation processes at high levels of vibrational excitation of molecules in the ground and triplet states are considered. For vapors of polyatomic molecules and their mixtures with foreign gases, the quantitative characteristics of the collisional exchange and the vibrational-energy transfer as well as the rates of intercombinational conversion ⇛ and triplet-triplet transfer are presented and their dependences on the vibrational-excitation level are discussed. Institute of Molecular and Atomic Physics of the National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 5, pp. 675–693, September–October, 1998.     

Field-free three-dimensional alignment of polyatomic molecules

We experimentally demonstrate field-free, three-dimensional alignment (FF3DA) of polyatomic asymmetric top molecules. We achieve FF3DA in sulfur dioxide gas using two time-delayed, orthogonally polarized, nonresonant, femtosecond laser pulses. Our method avoids the use of rotational revivals and is therefore more robust to temperature. The alignment is probed using time-delayed coincidence Coulomb explosion imaging. FF3DA will be important for all molecular imaging, dynamics, or spectroscopy experiments for which random alignment leads to a loss of information.     

Forbidden rotational spectra of polyatomic molecules

Some of the pure rotational transitions of polyatomic molecules that are forbidden according to the rigid rotor selection rules may acquire intensity by a centrifugal distortion mechanism, in which the intensity depends on the dipole derivatives and on the displacements in the normal coordinates produced by centrifugal distortion. The structures of the predicted spectra are discussed for nonpolar molecules belonging to the point groups D_3h, D_n (n > 2), D_2d, and T_d. Some of the calculated R-branch lines of methane are stronger than some of the lines of HD already observed in the same frequency range. For polar molecules extra contributions to the intensity must be considered and are exemplified for the Δk = ±3 transitions of C_3v molecules. These forbidden rotational transitions may have some astrophysical importance.     

Valence shell calculations on polyatomic molecules

Molecular quadrupole moments were calculated for some diatomic, symmetric top and small planar molecules by CNDO/2D and SCC methods. The results resemble those obtained by ab initio minimal basis set calculations and give a fairly good agreement with experimental data. The latter are closely reproduced only by ab initio extended basis set calculations indicating that molecular quadrupoles provide a sensitive test of the quality of the molecular wave functions. Flygare's empirical additivity rules for out-of-plane second moments of electronic charge distribution were rationalized in terms of CNDO/2 MO's over orthogonal AO's. In this model only one-centre terms are important and the sum of one-centre terms was approximately constant for the first-row atoms.     

Multiple photon infrared processes in polyatomic molecules

This paper reviews current understanding of the process of multiple photon excitation and dissociation of polyatomic molecules, whereby in the presence of an intense infrared laser field a molecule may absorb upwards of 30 photons. The application of this process to new photochemistry and in particular laser isotope separation will also be discussed.     

Effective Hamiltonian for polyatomic linear molecules

The leading terms of an effective Hamiltonian for a linear molecule in a given vibrational state are presented up to κ¹⁰T_v order of magnitude, whereby higher-order l-dependent terms such as $\text{H}\text{?}{}_{12.0}$, $\text{H}\text{?}{}_{8.0}$, and $\text{H}\text{?}{}_{8.2}$ have been neglected because in spectroscopic application they are of minor importance. This Hamiltonian therefore includes all those l-type interactions which could contribute to the fitting procedure, within a vibrational state where one or more bending vibrations are excited.     

Kinetics of dipole moments of polyatomic molecules

The relations that link the time dependences of the dipole moments of the ground and excited states of a molecular system whose charge distribution is nonstationary with the correlation functions of the shift of the absorption and emission spectra of this system are derived on the basis of of the well-known equations of solvatochromism. The calculated dependences of the kinetics of the dipole moments of the excited singlet states of dimethylaminobenzonitrile and 4-dimethylamino-4′-cyanostilbene in some polar solvents are presented.     

Pulsed Doppler-free two-photon spectroscopy of polyatomic molecules

Doppler-free two-photon electronic spectra of a large polyatomic molecule are recorded for the first time with pulsed laser radiation of near Fourier-transform limited bandwidth (Δv～100 MHz). The resolution obtained is sufficient to resolve individual rotational lines. Due to the high density of these rotational transitions a strong Doppler-broadened background is observed, which is, however, subtantially reduced by suitable choice of photon polarizations. Different vibronic bands of benzene (C₆H₆) are investigated and very accurate rotational constants are found.     

Sextic centrifugal distortion constants of polyatomic molecules

Detailed expressions, in terms of fundamental molecular parameters, are given for the sextic centrifugal distortion constants for a general polyatomic molecule. The calculation of these expressions is based on the Watson molecular vibrational-rotational hamiltonian using third and fourth-order ordinary perturbation theory. Numerical examples are given for the H₂S, SO₂ and NH₃ molecules. The calculated and observed sextic constants for these molecules are in good agreement.     

Fluorescence of binary mixtures of polyatomic molecules

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 50, No. 5, pp. 741–745, May, 1989.