A practical polarization propagator method devised for the treatment of valence electron excitations in atoms and molecules is presented. This method, referred to as (second-order) algebraic-diagrammatic construction (ADC(2)), allows for a theoretical description of single and double excitations consistently through second and first order, respectively, of perturbation theory. The computational scheme is essentially an eigenvalue problem of a Hermitian secular matrix defined with respect to the space of singly and doubly excited configurations. The configuration space is smaller (more compact) than that of comparable configuration interaction (CI) expansions and the method leads to size-consistent results. The performance of the ADC(2) method is tested in exemplary applications to Ne, Ar and CO, where detailed comparison can be made with experiment and previous theoretical results. While the accuracy of the absolute excitation energies is only moderate, a very satisfactory description is obtained for the relative energies and, in particular, for the spectral intensities. Aspects related to the Thomas-Reiche-Kuhn sum rule and the equivalence of the dipole-length and dipole-velocity forms of the transition moments are discussed. Due to the relatively small computational expense and the possibility of a direct ADC(2) formulation this method should prove particularly useful in applications to large molecules.

Propagator methods provide a direct approach to energies and transition moments for (generalized) electronic excitations from the ground state, but they do not usually allow one to determine excited state wave functions and properties. Using a specific intermediate state representation (ISR) concept, we here show how this restriction can be overcome in the case of the algebraic-diagrammatic construction (ADC) propagator approach. In the ISR reformulation of the theory the basic ADC secular matrix is written as a representation of the Hamiltonian (or the shifted Hamiltonian) in terms of explicitly constructable states, referred to as intermediate (or ADC) states. Similar intermediate state representations can be derived for operators other than the Hamiltonian. Together with the ADC eigenvectors, the intermediate states give rise to an explicit formulation of the excited wave functions and allow one to calculate physical properties of excited states as well as transition moments for transitions between different excited states. As for the ground-state excitation energies and transition moments, the ADC excited state properties are size consistent so that the theory is suitable for applications to large systems. The established hierarchy of higher-order [ADC(n)] approximations, corresponding to systematic truncations of the IS configuration space and the perturbation-theoretical expansions of the ISR matrix elements, can readily be extended to the excited state properties. Explicit ISR matrix elements for arbitrary one-particle operators have been derived and coded at the second-order [ADC(2)] level of theory. As a first computational test of the method we have carried out ADC(2) calculations for singlet and triplet excited state dipole moments in H(2)O and HF, where comparison to full CI results can be made. The potential of the ADC(2) method is further demonstrated in an exploratory study of the excitation energies and dipole moments of the low-lying excited states of paranitroaniline. We find that four triplet states, T1-T4, and two singlet states, S1 and S2, lie (vertically) below the prominent charge transfer (CT) excitation, S3. The dipole moment of the S3 state (17.0D) is distinctly larger than that of the corresponding T3 triplet state (11.7D).

The complete valence shell photoelectron spectra of cytosine, thymine and adenine have been investigated experimentally and theoretically. Vertical ionization energies and spectral intensities have been evaluated using the many-body Green's function method, thereby enabling theoretical photoelectron spectra to be derived. In cytosine, the influence of tautomers and rotational conformers has been investigated. The calculated spectra display a satisfactory agreement with the experimental data and this has allowed most of the photoelectron bands to be assigned. Photoelectron asymmetry parameters have been determined from angle resolved spectra recorded with synchrotron radiation. The experimental data show that the electronic configuration of the five outer orbitals in cytosine, thymine and adenine is π, σ, π, σ, π. Vertical ionization energies have been measured for all the outer-valence orbitals even though some of the associated bands overlap significantly.

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The K-shell excitation spectra of the hydrides water, ammonia, and methane have been measured in photoabsorption experiments using synchrotron radiation in combination with a high-resolution monochromator. For the case of methane, in particular, a wealth of spectral detail is observed which was not accessible in previous studies. The measured excitation energies and relative intensities compare well with values calculated using a complete second-order approximation for the polarization propagator. In order to determine the extent of admixing of valence excitations (i.e., transitions into virtual 0 orbitals) to the Rydberg manifolds, the X-H bond lengths have been varied in the calculations. In the case of H20, the two lowest-energy bands are due to the 0 1s-4a&/3s and 0 1s-2b2/3p transitions and have strong valence character; their width indicates that both excitations are dissociative. The NH3 and ND3 spectra are also broad which is not only due to possible dissociation but also to unresolved vibrational fine structure (v2 mode) and a Jahn-Teller instability. Valence character is concentrated in the lowest excited state in the Rydberg ns manifold, but is distributed more uniformly over the np(e) manifold. The weak dipole-forbidden C 1s -3s ( a & ) transition in CH4 and CD4 is accompanied by vibrational structure due to the v4 mode, indicating that it derives its intensity from vibronic coupling with the C 1s-3p(t2) transition. The structure on the latter band is extremely complicated due to Jahn-Teller coupling and cannot be assigned at present, as is the case for the Rydberg transitions at higher energies. The higher np Rydberg excitations contain considerable valence character. PACS number(s): 33.20.Rm 35.20. -i I. INTRQDUCTIDNE-shell excitation of the CH4, NH3, and H20 molecules has been studied in the past using both electronenergy-loss spectroscopy (EELS) [1 -4] and x-ray absorption spectroscopy [5 -9). Although the spectral resolution obtained with the latter technique has generally been rather modest and could not match that of EELS, recent advances in grazing-incidence monochromator design [10 -14] have resulted in a dramatic improvement of resolution with the "optical" approach. This has been shown in a number of high-resolution K-shell excitation spectra of small molecules reported recently (e.g. , ). In the present paper we describe measurements of the photoabsorption spectrum of gas phase H20, NH3, and CH4 in the near-E-edge region at a resolution sufficiently high to reveal directly the spectral line shape. To substantiate the assignments we have also calculated excitation energies and oscillator strengths using a polarization propagator method [20].In the virtual orbital spectrum of these hydrides and other saturated molecules one expects antibonding valence-type (cr ) orbitals which are the counterparts of the occupied bonding X-H orbitals. An important question is to what extent this antibonding valence character appears in the excitation spectrum. In most of the earlier E-shell studies on the h...

The O, N, and C 1s core level photoemission spectra of the nucleobases cytosine and uracil have been measured in the vapor phase, and the results have been interpreted via theoretical calculations. Our calculations accurately predict the relative binding energies of the core level features observed in the experimental photoemission results and provide a full assignment. In agreement with previous work, a single tautomer of uracil is populated at 405 K, giving rise to relatively simple spectra. At 450 K, three tautomers of cytosine, one of which may consist of two rotamers, are identified, and their populations are determined. This resolves inconsistencies between recent laser studies of this molecule in which the rare imino-oxo tautomer was not observed and older microwave spectra in which it was reported.

An earlier proposed propagator method for the treatment of molecular ionization is tested in first applications. The method referred to as the non-Dyson third-order algebraic-diagrammatic construction [nD-ADC(3)] approximation for the electron propagator represents a computationally promising alternative to the existing Dyson ADC(3) method. The advantage of the nD-ADC(3) scheme is that the (N+/-1)-electronic parts of the one-particle Green's function are decoupled from each other and the corresponding equations can be solved separately. For a test of the method the nD-ADC(3) results for the vertical ionization transitions in C(2)H(4), CO, CS, F(2), H(2)CO, H(2)O, HF, N(2), and Ne are compared with available experimental and theoretical data including results of full configuration interaction (FCI) and coupled cluster computations. The mean error of the nD-ADC(3) ionization energies relative to the experimental and FCI results is about 0.2 eV. The nD-ADC(3) method, scaling as n(5) with the number of orbitals, requires the solution of a relatively simple Hermitian eigenvalue problem. The method renders access to ground-state properties such as dipole moments. Moreover, also one-electron properties of (N+/-1) electron states can now be studied as a consequence of a specific intermediate-state representation (ISR) formulation of the nD-ADC approach. Corresponding second-order ISR equations are presented.

An efficient third-order propagator method to compute ionization potentials and electron affinities of atoms and molecules is presented. The development is based on the algebraic diagrammatic construction ͑ADC͒ representing a specific reformulation of the diagrammatic perturbation series of the electron propagator G͑͒. In contrast with previous approximation schemes, relying on the Dyson equation and approximations for the self-energy part, the ADC procedure here is applied directly to the (Nϯ1)-electron parts G Ϫ () and G ϩ (), respectively, of the electron propagator. This leads to decoupled secular equations for the ionization energies ((NϪ1)-electron part͒ and electron affinities ((Nϩ1)-electron part͒, respectively. In comparison with the Dyson-type approach, there is a substantial reduction of the secular matrix dimension opposed by a small additional expense in computing some second-and third-order contributions to the secular matrix elements. The relationship of the non-Dyson ADC͑3͒ method to coupled cluster methods is outlined.