Effect of absolute laser phase on reaction paths in laser-induced chemical reactions

Potential surfaces, dipole moments, and polarizabilities are calculated by ab initio methods [unrestricted MP2(full)/6-311++G(2d,2p)] along the reaction paths of the F+CH4 and Cl+CH4 reaction systems. It is found that in general dipole moments and polarizabilities exhibit peaks near the transition state. In the case of X=F these peaks are on the products side and in the case of X=Cl they are on the reactants side indicating an early transition state in the case of fluorine and a late transition state in the case of chlorine. An analysis of the geometric changes along the reaction paths reveals a one-to-one correspondence between the peaks in the electric properties and peaks in the rate of change of certain internal geometric coordinates along the reaction path. Interaction with short infrared intense laser fields pulses leads to the possibility of interferences between the dipole and polarizability laser-molecule interactions as a function of laser phase. The larger dipole moment in the Cl+CH4 reaction can lead to the creation of deep wells (instead of energy barriers) and new strongly bound states in the transition state region. This suggests possible coherent control of the reaction path as a function of the absolute phase of the incident field, by significant modification of the potential surfaces along the reaction path and, in particular, in the transition state region.     

Theoretical study of isomerization and dissociation of acetylene dication in the ground and excited electronic states

Ab initio calculations employing the configuration interaction method including Davidson's corrections for quadruple excitations have been carried out to unravel the dissociation mechanism of acetylene dication in various electronic states and to elucidate ultrafast acetylene-vinylidene isomerization recently observed experimentally. Both in the ground triplet and the lowest singlet electronic states of C2H2(2+) the proton migration barrier is shown to remain high, in the range of 50 kcal/mol. On the other hand, the barrier in the excited 2 3A" and 1 3A' states decreases to about 15 and 34 kcal/mol, respectively, indicating that the ultrafast proton migration is possible in these states, especially, in 2 3A", even at relatively low available vibrational energies. Rice-Ramsperger-Kassel-Marcus calculations of individual reaction-rate constants and product branching ratios indicate that if C2H(2)2+ dissociates from the ground triplet state, the major reaction products should be CCH+(3Sigma-)+H+ followed by CH+(3Pi)+CH+(1Sigma+) and with a minor contribution (approximately 1%) of C2H+(2A1)+C+(2P). In the lowest singlet state, C2H+(2A1)+C+(2P) are the major dissociation products at low available energies when the other channels are closed, whereas at Eint>5 eV, the CCH+(1A')+H+ products have the largest branching ratio, up to 70% and higher, that of CH+(1Sigma+)+CH+(1Sigma+) is in the range of 25%-27%, and the yield of C2H++C+ is only 2%-3%. The calculated product branching ratios at Eint approximately 17 eV are in qualitative agreement with the available experimental data. The appearance thresholds calculated for the CCH++H+, CH++CH+, and C2H++C+ products are 34.25, 35.12, and 34.55 eV. The results of calculations in the presence of strong electric field show that the field can make the vinylidene isomer unstable and the proton elimination spontaneous, but is unlikely to significantly reduce the barrier for the acetylene-vinylidene isomerization and to render the acetylene configuration unstable or metastable with respect to proton migration.     

A phase I, randomized study of combined IL-2 and therapeutic immunisation with antiretroviral therapy

Background  

Fully functional HIV-1-specific CD8 and CD4 effector T-cell responses are vital to the containment of viral activity and disease progression. These responses are lacking in HIV-1-infected patients with progressive disease. We attempted to augment fully functional HIV-1-specific CD8 and CD4 effector T-cell responses in patients with advanced chronic HIV-1 infection.     

Scattering theory of one and two-photon molecular processes

Using a perturbation expansion of the transition operator T, a scattering theory of one and two-photon processes is developed. Distinction is made between Franck-Condon and Herzberg-Teller effects. The influence of each effect is analysed for vibrational and electronic absorption and finally for Raman scattering.     

Laser induced preassociation in the presence of natural predissociation

Laser induced predissociation and its inverse, radiative preassociation are examined in the presence of natural (intrinsic) molecular predissociation. Quantum interferences will occur between the two processes, inducing optical windows in the energy transfer between the radiative channel and the natural predissociation channel. The radiative preassociation can serve as an efficient method of energy transfer to the predissociative channel.     

Analytic and numerical approach to multidimensional predissociation and resonance Raman scattering

Scattering theory is used to show that resonance Raman scattering and predissociation probabilities for multidimensional systems can be obtained from numerical solutions of the appropriate scattering coupled equations. Analytic results are presented for two-dimensional systems in terms of Airy functions. These analytic results are used to verify the coupled equations approach. An example is presented for the resonant photon scattering by an electronic state with one bound and one dissociative mode.     

Effect of nuclear motion on molecular high-order harmonics and on generation of attosecond pulses in intense laser pulses

We calculate harmonic spectra and shapes of attosecond-pulse trains using numerical solutions of Non-Born-Oppenheimer time-dependent Shr?dinger equation for 1D H2 molecules in an intense laser pulse. A very strong signature of nuclear motion is seen in the time profiles of high-order harmonics. In general the nuclear motion shortens the part of the attosecond-pulse train originating from the first electron contribution, but it may enhance the second electron contribution for longer pulses. The shape of time profiles of harmonics can thus be used for monitoring the nuclear motion.     

Transition state theory for laser-driven reactions

Recent developments in transition state theory brought about by dynamical systems theory are extended to time-dependent systems such as laser-driven reactions. Using time-dependent normal form theory, the authors construct a reaction coordinate with regular dynamics inside the transition region. The conservation of the associated action enables one to extract time-dependent invariant manifolds that act as separatrices between reactive and nonreactive trajectories and thus make it possible to predict the ultimate fate of a trajectory. They illustrate the power of our approach on a driven Henon-Heiles system, which serves as a simple example of a reactive system with several open channels. The present generalization of transition state theory to driven systems will allow one to study processes such as the control of chemical reactions through laser pulses.