Three-photon resonant four-photon ionization of H_2 via the C^1 ∏_u state

Ab initio calculations are presented for the vibrational branching ratios in three-photon resonant four-photon ionization of H_2 via the C^1Π_u state. Energy and internuclear distance dependences of the boundfree electronic transition matrix element are explicitly included to estimate deviations from the Franck-Condon approximation. While our calculated branching ratios confirm certain important trends seen experimentally, some differences remain

Photoionization cross sections of rovibrational levels of the B^1Σ^+_u state of H_2

We report theoretical cross sections for direct photoionization of specific rovibrational levels of the B ^1Σ^+_u electronic state of H_2. The calculated cross sections differ considerably from values recently determined by resonant enhanced multiphoton ionization (REMPI) studies. In an attempt to understand the disagreement, we analyze in detail the REMPI dynamics and find that the multiphoton ionization probability is extremely sensitive to the spatial and temporal profiles of the laser pulses. Accurate characterization of laser profiles and their jitter is therefore necessary for a comparison between theory and experiment

An equations of motion approach for open shell systems

A straightforward scheme is developed for extending the equations of motion formalism to systems with simple open shell ground states. Equations for open shell random phase approximation (RPA) are given for the cases of one electron outside of a closed shell in a nondegenerate molecular orbital and for the triplet ground state with two electrons outside of a closed shell in degenerate molecular orbitals. Applications to other open shells and extension of the open shell EOM to higher orders are both straightforward. Results for the open shell RPA for lithium atom and oxygen molecule are given

(2+1) resonant enhanced multiphoton ionization of H_2 via the E, F^(1)Σ^+_g state

In this paper, we report the results of ab initio calculations of photoelectron angular distributions and vibrational branching ratios for the (2+1) REMPI of H_2 via the E, F^(1)Σ^+_g state, and compare these with the experimental data of Anderson et al. [Chem. Phys. Lett. 105, 22 (1984)]. These results show that the observed non‐Franck–Condon behavior is predominantly due to the R dependence of the transition matrix elements, and to a lesser degree to the energy dependence. This work presents the first molecular REMPI study employing a correlated wave function to describe the Rydberg–valence mixing in the resonant intermediate state

Shape resonances in the photoionization of cyanogen

We have studied the photoionization cross sections and photoelectron asymmetry parameters for ionization of the 1pig(X 2Pig), 5sigmag(A 2Sigma + g), and 4sigmau(B 2Sigma + u) levels of cyanogen using frozen-core Hartree–Fock photoelectron continuum orbitals. The main purpose of these studies has been to extend our understanding of the dynamics of shape resonances from earlier studies of diatomic and smaller polyatomic molecules to a larger polyatomic system. The results do, in fact, reveal a rich shape resonant structure in the electronic continuum of this polyatomic system. There is a low-energy sigmau resonance which, as expected, is the C–C analog of the l=3 shape resonance seen in N2(3sigma - 1g) and several other diatomics. In contrast to this diatomic-like behavior, the presence of the two CN groups in C2N2 results in a second sigmau and a sigmag resonance corresponding to linear combinations of a l=3 shape resonance localized on the CN sites. Moreover, our results also show a pronounced shape resonant behavior in the piu continuum, which, to our knowledge, has not been seen in smaller molecules

Some applications of excited-state-excited-state transition densities

We derive an approximation for transition moments between excited states consistent with the approximations and assumptions normally used to obtain transition moments betwen the ground and excited states in the random-phase approximation and its higher-order approximations. We apply the result to the calculation of the photoionization cross sections of the 23S and 21S metastable states of helium by a numerical analytical continuation of the frequency-dependent polarizability. The procedure completely avoids the need for continuum basis functions. The cross sections agree well with the results of other calculations. We also predict an accurate two-photon decay rate for the 21S metastable state of helium. The entire procedure is immediately applicable to several problems involving photoionization of metastable states of molecules

Dynamics of Single- and Multi-photon Ionisation Processes in Molecules

Single-photon ionisation and resonant multiphoton ionisation studies, which can now be carried out using synchrotron radiation and pulsed dye lasers respectively, are providing important dynamical information on molecular photoionisation. In this paper we discuss some results of our recent studies of several, single- and multi-photon ionisation processes in molecules. The results will be taken from our studies of (i) single-photon ionisation of linear molecules with emphasis on the role of shape and autoionising resonances on these cross· sections, (ii) photoionisation from oriented NiCO as a simple but realistic model of photoemission in adsorbate-substrate systems, and (iii) resonant multiphoton ionisation of H_2

Relaxation effects in molecular K-shell photoionization

The effects of core relaxation on the shape-resonant K-shell photoionization cross section in N2 are shown to be very significant. Cross relaxation produces substantial broadening and shifting of the shape resonance to higher energy. The results suggest that the frozen-core approximation may not be an appropriate model for K-shell photoionization involving a low-energy shape resonance

Photoelectron spectroscopy of excited molecular states

Results of studies of ion rotational and vibrational distributions for resonance enhanced multiphoton ionization are discussed