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Register a new userExcited states of linear polyenes
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Added by
Dr Robert J. Bursill
Publication date
2001
fields
Physics
and research's language is
English
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We present density matrix renormalisation group calculations of the Pariser- Parr-Pople-Peierls model of linear polyenes within the adiabatic approximation. We calculate the vertical and relaxed transition energies, and relaxed geometries for various excitations on long chains. The triplet (3Bu+) and even- parity singlet (2Ag+) states have a 2-soliton and 4-soliton form, respectively, both with large relaxation energies. The dipole-allowed (1Bu-) state forms an exciton-polaron and has a very small relaxation energy. The relaxed energy of the 2Ag+ state lies below that of the 1Bu- state. We observe an attraction between the soliton-antisoliton pairs in the 2Ag+ state. The calculated excitation energies agree well with the observed values for polyene oligomers; the agreement with polyacetylene thin films is less good, and we comment on the possible sources of the discrepencies. The photoinduced absorption is interpreted. The spin-spin correlation function shows that the unpaired spins coincide with the geometrical soliton positions. We study the roles of electron-electron interactions and electron-lattice coupling in determining the excitation energies and soliton structures. The electronic interactions play the key role in determining the ground state dimerisation and the excited state transition energies.
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We propose a novel approach to calculate dynamical processes at ultrafast time scale in molecules in which vibrational and electronic motions are strongly mixed. The relevant electronic orbitals and their interactions are described by a Hubbard model, while electron-phonon interaction terms account for the bond length dependence of the hopping and the change in ionic radii with valence charge. The latter term plays a crucial role in the non-adiabatic internal conversion process of the molecule. The time resolved photoelectron spectra are in good qualitative agreement with experiments.
We present a linear-response formulation of density cumulant theory (DCT) that provides a balanced and accurate description of many electronic states simultaneously. In the original DCT formulation, only information about a single electronic state (usually, the ground state) is obtained. We discuss the derivation of linear-response DCT, present its implementation for the ODC-12 method (LR-ODC-12), and benchmark its performance for excitation energies in small molecules (N$_2$, CO, HCN, HNC, C$_2$H$_2$, and H$_2$CO), as well as challenging excited states in ethylene, butadiene, and hexatriene. For small molecules, LR-ODC-12 shows smaller mean absolute errors in excitation energies than equation-of-motion coupled cluster theory with single and double excitations (EOM-CCSD), relative to the reference data from EOM-CCSDT. In a study of butadiene and hexatriene, LR-ODC-12 correctly describes the relative energies of the singly-excited $1^1mathrm{B_{u}}$ and the doubly-excited $2^1mathrm{A_{g}}$ states, in excellent agreement with highly accurate semistochastic heat-bath configuration interaction results, while EOM-CCSD overestimates the energy of the $2^1mathrm{A_{g}}$ state by almost 1 eV. Our results demonstrate that linear-response DCT is a promising theoretical approach for excited states of molecules.
The most popular electronic structure method, the linear muffin-tin orbital method (LMTO), in its full-potential (FP) and relativistic forms has been extended to calculate the spectroscopic properties of materials form first principles, i.e, optical spectra, x-ray magnetic circular dichroism (XMCD) and magneto-optical kerr effect (MOKE). The paper describes an overview of the FP-LMTO basis set and the calculation of the momentum matrix elements. Some applications concerning the computation of optical properties of semiconductors and XMCD spectra of transition metal alloys are reviewed.
We report four narrow peaks in the $Xi_b^0K^-$ mass spectrum obtained using $pp$ collisions at center-of-mass energies of 7, 8 and 13 TeV, corresponding to a total integrated luminosity of 9 fb$^{-1}$ recorded by the LHCb experiment. Referring to these states by their mass, the mass values are begin{align*} m(Omega_b(6316)^-) &= 6315.64pm0.31pm0.07pm0.50 {rm MeV}, m(Omega_b(6330)^-) &= 6330.30pm0.28pm0.07pm0.50 {rm MeV}, m(Omega_b(6340)^-) &= 6339.71pm0.26pm0.05pm0.50 {rm MeV}, m(Omega_b(6350)^-) &= 6349.88pm0.35pm0.05pm0.50 {rm MeV}, end{align*}where the uncertainties are statistical, systematic and the last is due to the knowledge of the $Xi_b^0$ mass. The natural widths of the three lower mass states are consistent with zero, and the 90% confidence-level upper limits are determined to be ${Gamma(Omega_b(6316)^-)<2.8}$ MeV, ${Gamma(Omega_b(6330)^-)<3.1}$ MeV and ${Gamma(Omega_b(6340)^-)<1.5}$ MeV. The natural width of the $Omega_b(6350)^-$ peak is $1.4^{+1.0}_{-0.8}pm0.1$ MeV, which is 2.5$sigma$ from zero and corresponds to an upper limit of 2.8 MeV. The peaks have local significances ranging from 3.6$sigma$ to 7.2$sigma$. After accounting for the look-elsewhere effect, the significances of the $Omega_b(6316)^-$ and $Omega_b(6330)^-$ peaks are reduced to 2.1$sigma$ and 2.6$sigma$ respectively, while the two higher mass peaks exceed 5$sigma$. The observed peaks are consistent with expectations for excited $Omega_b^-$ resonances.
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