Theory of anharmonically modified Coriolis coupling in the S1 state of benzene and relation to experiment

Avoided crossings between quasidegenerate rovibrational states in the Doppler-free two-photon excitation of the 141 mode in the S1 excited state of benzene are treated theoretically. Two sets of avoided crossings in plots of spectral line frequency vs J at a given K and DeltaK have been reported experimentally between an initially prepared "light" state (141 in zeroth order) and dark states, namely, one which in zeroth order is a 51101161 state, the other being in zeroth order a 62111 and/or possibly a 31161 state, implicated earlier by Neusser et al. The identification of these states makes the phenomenon an excellent candidate for treatment of the avoided crossing via a Van Vleck transformation, no other basis set states being needed for the diagonalization in order to extract the important features. Two successive transformations are used for handling direct coupling and coupling via virtual states. The dominant calculated contribution to the coupling is, jointly, Coriolis plus cubic–cubic anharmonic interactions between vibrational modes.Playing less of a role are Coriolis terms in which the inverse moment of inertia tensor is expanded up to quadratic terms in the coordinates. There results a 5×5 (for coupling to 51101161 ) and a 3×3 (for coupling to 62111 or 31161 ) matrix of the transformed Hamiltonian, each of which can also be described, if desired, to a very good approximation by a 2×2 matrix. The coupling element V0 and the difference of the rotational constants for the light and dark states (DeltaB) are obtained from the plots of line position vs J(J+1) obtained. For the 141 to 51101161 and for the 141 to 62111 couplings the theoretical results are in reasonable agreement with the experimental results, no adjustable parameters being employed. For a coupling of 141 to 31161 the calculated V0 would be much too high compared with experiment (a factor of 10), the coupling involving the exchange of only three instead of four vibrational quanta. A situation in which the 141 state is coupled to the 62111 state to yield an avoided crossing and off-resonantly coupled to the 31161 state would be consistent with some experimental results and not affect the reasonable agreement of the slope difference and splitting for the avoided crossing plots

Theory of fluorescence excitation spectra using anharmonic-coriolis coupling in S1 and internal conversion to S0. I. General formalism

A treatment of one- or two-photon fluorescence excitation spectra is described using the vibration–rotation coupling of zeroth order states in the excited electronic state and nonadiabatic coupling to the ground state. Using perturbation theory, experimental harmonic frequencies, an anharmonic force field, and various theoretical Coriolis coupling constants, a quasistationary molecular eigenstate in an excited electronic state S1 is first calculated. The S1 eigenstate is then coupled via the nonadiabatic nuclear kinetic energy operator (internal conversion) to rovibronic states in the ground state manifold, the latter states approximated in a simple manner. A search algorithm is used to select the S1 dark states and the S0 states. Both the perturbation theory coefficient and the Franck–Condon factors are employed in the evaluation function used in the search. The results are applied in part II to the channel three problem in benzene

Circadian Entrainment Triggers Maturation of Human In Vitro Islets

Stem-cell-derived tissues could transform disease research and therapy, yet most methods generate functionally immature products. We investigate how human pluripotent stem cells (hPSCs) differentiate into pancreatic islets in vitro by profiling DNA methylation, chromatin accessibility, and histone modification changes. We find that enhancer potential is reset upon lineage commitment and show how pervasive epigenetic priming steers endocrine cell fates. Modeling islet differentiation and maturation regulatory circuits reveals genes critical for generating endocrine cells and identifies circadian control as limiting for in vitro islet function. Entrainment to circadian feeding/fasting cycles triggers islet metabolic maturation by inducing cyclic synthesis of energy metabolism and insulin secretion effectors, including antiphasic insulin and glucagon pulses. Following entrainment, hPSC-derived islets gain persistent chromatin changes and rhythmic insulin responses with a raised glucose threshold, a hallmark of functional maturity, and function within days of transplantation. Thus, hPSC-derived tissues are amenable to functional improvement by circadian modulation

Ab initio synthesis of the ozone ultraviolet continuum

Potential energy surfaces for the ground and excited electronic states responsible for the Hartley continuum of ozone are used to obtain quadratic, cubic, and quartic force constants. Vibrational dependence of rotational constants to sixth order is calculated by perturbation theory. The spectroscopic constants enable computation of rovibronic energy levels. Overlap of ground state and excited state perturbed vibrational wave functions yield Franck–Condon factors. Electric dipole allowed rovibronic transitions are generated under the Ir representation. The entire set of results generate the ultraviolet absorption spectrum. It is shown that inclusion of anharmonic terms in the vibrational Hamiltonian has a small effect upon the final spectrum, whereas rotational broadening plays a greater role in achieving agreement with experiment.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/69598/2/JCPSA6-86-10-5329-1.pd

Hole spin polarization in GaAlAs:Mn structures

A self-consistent calculation of the electronic properties of GaAlAs:Mn magnetic semiconductor quantum well structures is performed including the Hartree term and the sp-d exchange interaction with the Mn magnetic moments. The spin polarization density is obtained for several structure configurations. Available experimental results are compared with theory.Comment: 4 page

Nuclear medicine in oral and maxillofacial diagnosis: a review for the practicing dental professional

Nuclear medicine studies often play a significant role in the diagnosis and treatment of oral and maxillofacial diseases. While not commonly used in everyday dental practice, the dental provider should have a conversational knowledge of these imaging modalities and understand the indications and limitations of these studies. The purpose of this review is to discuss the nuclear medicine studies that have applications in the head and neck region as well as their indications, limitations, and diagnostic conclusions that can be drawn from these studies