Intramolecular Radiationless Transitions
TL;DR: In this paper, the authors considered a theory for intramolecular radiationless transitions in an isolated molecule and derived the validity criteria for the occurrence of an unimolecular radii-less transition and for exponential decay.
Abstract: In this paper we consider a theory for intramolecular radiationless transitions in an isolated molecule. The Born–Oppenheimer zero‐order excited states are not pure in view of configuration interaction between nearly degenerate zero‐order states, leading to the broadening of the excited state, the line shape being Lorentzian. The optically excited state can be described in terms of a superposition of molecular eigenstates, and the resulting wavefunction exhibits an exponential nonradiative decay. The linewidth and the radiationless lifetime are expressed in terms of a single molecular parameter, that is the square of the interaction energy between the zero‐order state and the manifold of all vibronic states located within one energy unit around that state. The validity criteria for the occurrence of an unimolecular radiationless transition and for exponential decay in an isolated molecule are derived. Provided that the density of vibrational states is large enough (i.e., exceeds the reciprocal of the interaction matrix element) radiationless transitions are expected to take place. The gross effects of molecular structure on the relevant molecular parameters are discussed.
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TL;DR: In this article, a unified treatment of non-radiative decay processes in large molecules which involve either electronic relaxation between two electronic states or unimolecular rearrangeme(s) is presented.
Abstract: In this paper we present a unified treatment of non-radiative decay processes in large molecules which involve either electronic relaxation between two electronic states or unimolecular rearrangeme...
2,060 citations
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TL;DR: The nature and dynamics of the singlet excited electronic states created in nucleic acids and their constituents by UV light are reviewed, finding that these states are highly stable to photochemical decay, perhaps as a result of selection pressure during a long period of molecular evolution.
Abstract: The scope of this review is the nature and dynamics of the singlet excited electronic states created in nucleic acids and their constituents by UV light. Interest in the UV photochemistry of nucleic acids has long been the motivation for photophysical studies of the excited states, because these states are at the beginning of the complex chain of events that culminates in photodamage. UV-induced damage to DNA has profound biological consequences, including photocarcinogenesis, a growing human health problem.1-3 Sunlight, which is essential for life on earth, contains significant amounts of harmful UV (λ < 400 nm) radiation. These solar UV photons constitute one of the most ubiquitous and potent environmental carcinogens. This extraterrestrial threat is impressive for its long history; photodamage is as old as life itself. The genomic information encoded by these biopolymers has been under photochemical attack for billions of years. It is not surprising then that the excited states of the nucleic acid bases (see Chart 1), the most important UV chromophores of nucleic acids, are highly stable to photochemical decay, perhaps as a result of selection pressure during a long period of molecular evolution. This photostability is due to remarkably rapid decay pathways for electronic energy, which are only now coming into focus through femtosecond laser spectroscopy. The recently completed map of the human genome and the ever-expanding crystallographic database of nucleic acid structures are two examples that illustrate the richly detailed information currently available about the static properties of nucleic acids. In contrast, much less is known about the dynamics of these macromolecules. This is particularly true of the dynamics of the excited states that play a critical role in DNA photodamage. Efforts to study nucleic acids by time-resolved spectroscopy have been stymied by the apparent lack of suitable fluorophores. In contrast, dynamical spectroscopy of proteins has flourished thanks to intrinsically fluorescent amino acids such as tryptophan, tyrosine, and phenylalanine.4 The primary UVabsorbing constituents of nucleic acids, the nucleic acid bases, have vanishingly small fluorescence quantum yields under physiological conditions of temperature and pH.5 In fact, the bases were frequently described as “nonfluorescent” in the early literature. * To whom correspondence should be addressed. E-mail: kohler@ chemistry.ohio-state.edu. Phone: (614) 688-3944. Fax: (614) 2921685. 1977 Chem. Rev. 2004, 104, 1977−2019
1,115 citations
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TL;DR: A critical review of light-driven interfacial charge-transfer reactions of transition-metal compounds anchored to mesoporous, nanocrystalline TiO2 (anatase) thin films is described.
Abstract: A critical review of light-driven interfacial charge-transfer reactions of transition-metal compounds anchored to mesoporous, nanocrystalline TiO2 (anatase) thin films is described. The review highlights molecular insights into metal-to-ligand charge transfer (MLCT) excited states, mechanisms of interfacial charge separation, inter- and intra-molecular electron transfer, and interfacial charge-recombination processes that have been garnered through various spectroscopic and electrochemical techniques. The relevance of these processes to optimization of solar-energy-conversion efficiencies is discussed (483 references).
1,066 citations
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TL;DR: The underlying physical principles--light absorption, energy transfer, radiative and nonradiative excited-state decay, electron transfer, proton-coupled electronTransfer, and catalysis--are outlined with an eye toward their roles in molecular assemblies for energy conversion.
Abstract: The goal of artificial photosynthesis is to use the energy of the sun to make high-energy chemicals for energy production. One approach, described here, is to use light absorption and excited-state electron transfer to create oxidative and reductive equivalents for driving relevant fuel-forming half-reactions such as the oxidation of water to O2 and its reduction to H2. In this "integrated modular assembly" approach, separate components for light absorption, energy transfer, and long-range electron transfer by use of free-energy gradients are integrated with oxidative and reductive catalysts into single molecular assemblies or on separate electrodes in photelectrochemical cells. Derivatized porphyrins and metalloporphyrins and metal polypyridyl complexes have been most commonly used in these assemblies, with the latter the focus of the current account. The underlying physical principles--light absorption, energy transfer, radiative and nonradiative excited-state decay, electron transfer, proton-coupled electron transfer, and catalysis--are outlined with an eye toward their roles in molecular assemblies for energy conversion. Synthetic approaches based on sequential covalent bond formation, derivatization of preformed polymers, and stepwise polypeptide synthesis have been used to prepare molecular assemblies. A higher level hierarchial "assembly of assemblies" strategy is required for a working device, and progress has been made for metal polypyridyl complex assemblies based on sol-gels, electropolymerized thin films, and chemical adsorption to thin films of metal oxide nanoparticles.
916 citations
References
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01 Jan 1959
TL;DR: In this paper, the authors discuss various topics about optics, such as geometrical theories, image forming instruments, and optics of metals and crystals, including interference, interferometers, and diffraction.
Abstract: The book is comprised of 15 chapters that discuss various topics about optics, such as geometrical theories, image forming instruments, and optics of metals and crystals. The text covers the elements of the theories of interference, interferometers, and diffraction. The book tackles several behaviors of light, including its diffraction when exposed to ultrasonic waves.
19,815 citations
[...]
01 Oct 1999
TL;DR: In this article, the authors discuss various topics about optics, such as geometrical theories, image forming instruments, and optics of metals and crystals, including interference, interferometers, and diffraction.
Abstract: The book is comprised of 15 chapters that discuss various topics about optics, such as geometrical theories, image forming instruments, and optics of metals and crystals. The text covers the elements of the theories of interference, interferometers, and diffraction. The book tackles several behaviors of light, including its diffraction when exposed to ultrasonic waves.
19,503 citations
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TL;DR: In this paper, a theoretical analysis of the shape of the 2s2p^{1}P resonance of He observed in the inelastic scattering of electrons is presented. But the analysis is restricted to the case of one discrete level with two or more continua and of a set of discrete levels with one continuum.
Abstract: The interference of a discrete autoionized state with a continuum gives rise to characteristically asymmetric peaks in excitation spectra. The earlier qualitative interpretation of this phenomenon is extended and revised. A theoretical formula is fitted to the shape of the $2s2p^{1}P$ resonance of He observed in the inelastic scattering of electrons. The fitting determines the parameters of the $2s2p^{1}P$ resonance as follows: $E=60.1$ ev, $\ensuremath{\Gamma}\ensuremath{\sim}0.04$ ev, $f\ensuremath{\sim}2 \mathrm{to} 4\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}3}$. The theory is extended to the interaction of one discrete level with two or more continua and of a set of discrete levels with one continuum. The theory can also give the position and intensity shifts produced in a Rydberg series of discrete levels by interaction with a level of another configuration. The connection with the nuclear theory of resonance scattering is indicated.
8,210 citations
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01 Jan 1954
TL;DR: Born and Huang's classic work on the dynamics of crystal lattices was published over thirty years ago, and it remains the definitive treatment of the subject as mentioned in this paper. But it is not the most complete work on crystal lattice dynamics.
Abstract: Although Born and Huang's classic work on the dynamics of crystal lattices was published over thirty years ago, the book remains the definitive treatment of the subject. It begins with a brief introduction to atomic forces, lattice vibrations and elasticity, and then breaks off into four sections. The first section deals with the general statistical mechanics of ideal lattices, leading to the electric polarizability and to the scattering of light. The second section deals with the properties of long lattice waves, the third with thermal properties, and the fourth with optical properties.
7,756 citations
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01 Jan 1932
TL;DR: Alfaro et al. as mentioned in this paper conservado en la Biblioteca del Campus de Mostoles de la Universidad Rey Juan Carlos (sign. 517.5 TIT THE).
Abstract: Original conservado en la Biblioteca del Campus de Mostoles de la Universidad Rey Juan Carlos (sign. 517.5 TIT THE).
2,695 citations