16 research outputs found
Science Classics
An essay on the impact of the works in the Imprints and Impressions: Milestones in Human Progress, an exhibition of rare books from the collection of Stuart Rose. Exhibition was held Sept. 29-Nov. 9, 2014, at the University of Dayton
Exhibition catalogue â Imprints and Impressions: Milestones in Human Progress
Exhibition catalogue for Imprints and Impressions: Milestones in Human Progress â Highlights from the Rose Rare Book Collection. Includes an introduction by Kathleen M. Webb, dean of University Libraries; essays about the impact of the exhibition\u27s books on modern inquiry, the humanities, the sciences, and the social sciences; and photographs of the works in the exhibit.https://ecommons.udayton.edu/rosebk_supplemental/1000/thumbnail.jp
Nonlinear Optical Properties of Bacteriorhodopsin: Assignment of the Third-order Polarizability Based on Two-photon Absorption Spectroscopy
The third-order (pi) -electron polarizability, (gamma) (pi), of bacteriorhodopsin in the 0.0 - 1.2 eV optical region is assigned based on an analysis of the experimental two-photon properties of the low-lying singlet state manifold. The following selected values of (gamma) (pi) (units of 10-36 esu) are observed: (gamma) (0;0,0,0) equals 2482 +/- 327; (gamma) (-3(omega) ;(omega) ,(omega) ,(omega) ) equals 2976 +/- 385 ((omega) equals 0.25 eV), 5867 +/- 704 ((omega) = 0.5 eV), 14863 +/- 1614 ((omega) = 0.66 eV), 15817 +/- 2314 ((omega) equals 1.0 eV), 10755 +/- 1733 ((omega) equals 1.17 eV). The third-order polarizability of this protein which contains an all-trans retinyl protonated Schiff base chromophore with six double bonds, is comparable to that observed for much longer chain polyenes (for example, dodecapreno (beta) -carotene, a polyene with 19 double bonds, exhibits a third-order (pi) -electron polarizability at 0.66 eV of 17000 +/- 6000 X 10-36 esu. The authors attribute the enhanced third-order nonlinearity associated with the protein bound chromophore of bacteriorhodopsin to two mutually enhancing origins. First, the chromophore is protonated, and the resultant charge reorganization enhances the polarizability in a fashion that is similar to that known to occur for polaronic and bipolaronic chromophores. It is estimated that protonation generates a five-fold enhancement in (gamma) (pi). Second, the protein bound chromophore exhibits a large change in dipole moment upon excitation into the lowest-lying, strongly-allowed 1B*u+-like state ((Delta) (mu) = 13.5 D). The latter property is responsible for a Type III enhancement of the third-order polarizability, and yields at least a 20-fold increase in (gamma) (pi)
Origins of the Quantum Efficiency Duality In the Primary Photochemical Event of Bacteriorhodopsin
Experimental and theoretical evidence is presented which suggests that two distinct forms of light-adapted bacteriorhodopsin may exist. We propose that these two forms have characteristic photocycles with significantly different primary quantum yields. INDO-PSDCI molecular orbital procedures and semiempirical molecular dynamics simulations predict that one ground state geometry of bR undergoes photochemistry with a primary quantum yield, ÎŚ1, of ~ 0.27, and that a second ground state geometry, with a slightly displaced counterion, yields ÎŚ1 ~ 0.74. This theoretical model is supported by the observation that literature measurements of ÎŚ1 tend to fall into one of two categories- those that observe ÎŚ1 ~ 0.33 or below, and those that observe ÎŚ1 ~ 0.6 or above. The observation that all photostationary state measurements of the primary quantum yield give values near 0.3, and all direct measurements of the quantum yield result in values near 0.6, suggests that photochemical back reactions may select the bacteriorhodopsin conformation with the lower quantum yield. The two photocycles may have developed as a natural biological requirement that the bacterium have the capacity to adjust the efficiency of the photocycle in relation to the intensity of light and/or membrane electrochemical gradient
A Theoretical Investigation of the Oneâ and Twoâphoton Properties of Porphyrins
The oneâ and twoâphoton properties of free base porphin, free base porphin dianion, and the 2,4âsubstituted diformyl and divinyl analogs of these molecules are studied using a semiempirical SCFâMO formalism (CNDOâĎâSCFâMOâPSDCI) including extensive single and double configuration interaction. Strongly twoâphoton allowed states are predicted to lie in the Soret region as well as in the region between the Soret and visible bands. A number of the twoâphoton allowed states in the Soret region are predicted to have twoâphoton absorptivities exceeding 100Ă10â50 cm4âsâmoleculeâ1âphotonâ1. The calculations indicate that the visible (Q) states are well characterized by the four orbital model, whereas the Soret (B) states contain significant contributions from configurations comprised of other orbitals. The inclusion of extensive double configuration interaction significantly reduces the Soretâvisible (BâQ) splitting, increases the QxâQy splitting, and yields calculated oscillator strengths for the Qbands in better agreement with experiment than values calculated using single CI alone. The effects of conjugation into the porphyrin macrocycle are predicted to be more significant than inductive effects on macrocycle Ď orbitals due to substituent polarity. The ăQxârâS0ă and ăQyârâS0ă transition moment vectors are predicted to lie approximately through adjacent pyrrole rings in 2â and 4âmonoformyl free base porphin dianions and approximately through adjacent methine bridges in 2,4âdiformyl free base porphin dianion
EigenstateâSpecific Temperatures in TwoâLevel Paramagnetic Spin Lattices
Increasing interest in the thermodynamics of small and/or isolated systems, in combination with recent observations of negative temperatures of atoms in ultracold optical lattices, has stimulated the need for estimating the conventional, canonical temperature Tconvc of systems in equilibrium with heat baths using eigenstate-specific temperatures (ESTs). Four distinct ESTsâcontinuous canonical, discrete canonical, continuous microcanonical, and discrete microcanonicalâare accordingly derived for two-level paramagnetic spin lattices (PSLs) in external magnetic fields. At large N, the four ESTs are intensive, equal to Tconvc, and obey all four laws of thermodynamics. In contrast, for N \u3c 1000, the ESTs of most PSL eigenstates are non-intensive, differ from Tconvc, and violate each of the thermodynamic laws. Hence, in spite of their similarities to Tconvc at large N, the ESTs are not true thermodynamic temperatures. Even so, each of the ESTs manifests a unique functional dependence on energy which clearly specifies the magnitude and direction of their deviation from Tconvc; the ESTs are thus good temperature estimators for small PSLs. The thermodynamic uncertainty relation is obeyed only by the ESTs of small canonical PSLs; it is violated by large canonical PSLs and by microcanonical PSLs of any size. The ESTs of population-inverted eigenstates are negative (positive) when calculated using Boltzmann (Gibbs) entropies; the thermodynamic implications of these entropically induced differences in sign are discussed in light of adiabatic invariance of the entropies. Potential applications of the four ESTs to nanothermometers and to systems with long-range interactions are discussed
2022: Mark Masthay, Milestone Book Selection
Promotion to the rank of Professor, Department of Chemistryhttps://ecommons.udayton.edu/svc_milestone/1095/thumbnail.jp
Positive and Negative Temperatures in a Two-Level System: Thermodynamic and Statistical-Mechanical Perspectives
Transient negative temperature states have been reported for a range of systems having a finite number of energy levels. While such systems are rare and seem to contradict the common notion that temperature is always positive, they provide an effective platform for illustrating the relationship between the thermodynamic and statistical-mechanical formulations of temperature. In this article we present a set of calculations for a two-level system containing N particles (1 ⤠N ⤠â) that graphically illustrates the statistical nature of temperature as well as the fundamental equivalence of its thermodynamic and statistical-mechanical formulations. These calculations, which we have applied in our undergraduate- and graduate-level physical chemistry courses, provide pedagogically useful insights into the meaning of a variety of thermodynamic and statistical mechanical concepts that students frequently have difficulty grasping
Effects of Monoâ Versus Diâsubstitution of Conjugating Groups on the Electronic Structure of Porphyrins
Mono- and adjacent-pyrrole disubstituted porphin dianions (substituents either formyl or vinyl groups) are examined with a semi-empirical SCF MO formalism (CNDO Ď SCF PSDCI) which includes extensive single and double CI. Calculations predict that the presence of the second conjugating group on an adjacent pyrrole ring enhances the asymmetry introduced by the first group and that the magnitude and orientation of the transition-dipole moments are strongly dependent on the substituent groups
Nonlinear Optical Properties of Bacteriorhodopsin: Assignment of Second Order Hyperpolarizabilities of Randomly Oriented Systems Using Two-Photon Spectroscopy
We demonstrate that the second order hyperpolarizability of a randomly oriented molecule can be determined directly from two-photon spectroscopic measurements on the low-lying excited state manifold. Equations are derived which allow not only a determination of β, but also a determination of the error associated with the numerical method. We apply our two-photon technique to an analysis of the second order hyperpolarizability of light adapted bacteriorhodopsin. Our analysis of this protein in D2O at ambient temperature yields a value of β (= βxxx + (1/3)[βxyy + 2βyyx + βxzz + 2βzzx]) of (2250 Âą 240) Ă 10â30 cm5/esu for a laser wavelength of 1.06Îź (Nd:YAG fundamental). The large second-order nonlinear properties of bacteriorhodopsin are due primarily to the large change in dipole moment associated with excitation into the lowest-lying strongly allowed â1Bu +â Ď, Ď* state (ÎÎź = 13.5 Âą 0.8 D). We derive an equation which estimates Ίβδ, the ratio of the number of second harmonic photons generated by the system divided by the number of photons absorbed by the system via two-photon processes. Our analysis indicates that molecular doubters can be optimized by maximizing the oscillator strength of the low-lying charge transfer state (fso), the orientation angle of the transition dipole with the polarization of the laser flux, the sample length and the chromophore concentration. All of the above manipulations will also increase the efficiency of doubling, and thus optimization of these parameters is critical to overall doubling performance