First-principles

Harvey A N 1999 Applications of first-principles calculations to the correlation of water s second virial coefficient Proc. 13th Int. Conf of the Properties of Water and Steam (Toronto, 12-16 September 1999)... 

Radiation probes such as neutrons, x-rays and visible light are used to see the structure of physical systems tlirough elastic scattering experunents. Inelastic scattering experiments measure both the structural and dynamical correlations that exist in a physical system. For a system which is in thennodynamic equilibrium, the molecular dynamics create spatio-temporal correlations which are the manifestation of themial fluctuations around the equilibrium state. For a condensed phase system, dynamical correlations are intimately linked to its structure. For systems in equilibrium, linear response tiieory is an appropriate framework to use to inquire on the spatio-temporal correlations resulting from thennodynamic fluctuations. Appropriate response and correlation functions emerge naturally in this framework, and the role of theory is to understand these correlation fiinctions from first principles. This is the subject of section A3.3.2. 

Klippenstein S J, East ALL and Allen W D A 1994 First principles theoretical determination of the rate constant for the dissociation of singlet ketene J. Chem. Phys. 101 9198-201... 

Unlike the typical laser source, the zero-point blackbody field is spectrally white , providing all colours, CO2, that seek out all co - CO2 = coj resonances available in a given sample. Thus all possible Raman lines can be seen with a single incident source at tOp Such multiplex capability is now found in the Class II spectroscopies where broadband excitation is obtained either by using modeless lasers, or a femtosecond pulse, which on first principles must be spectrally broad [32]. Another distinction between a coherent laser source and the blackbody radiation is that the zero-point field is spatially isotropic. By perfonuing the simple wavevector algebra for SR, we find that the scattered radiation is isotropic as well. This concept of spatial incoherence will be used to explain a certain stimulated Raman scattering event in a subsequent section. 

Luce T A and Bennemann K H 1998 Nonlinear optical response of noble metals determined from first-principles electronic structures and wave functions calculation of transition matrix elements P/rys. Rev. B 58 15 821-6... 

The relative simplicity of tlie method and the penetrative nature of the x-rays, yield a technique that is sensitive to elements with Z > 10 down to a few parts per million (ppm) and can be perfonued quantitatively from first principles. The databases for PIXE analysis programs [21, 22 and 23] are typically so well developed as to include accurate fiindamental parameters, allowing the absolute precision of the technique to be around 3% for major elements and 10-20% for trace elements. A major factor m applying the PIXE teclmique is that the bombardmg energy of the... 

First-principles models of solid surfaces and adsorption and reaction of atoms and molecules on those surfaces range from ab initio quantum chemistry (HF configuration interaction (Cl), perturbation theory (PT), etc for details see chapter B3.1 ) on small, finite clusters of atoms to HF or DFT on two-dimensionally infinite slabs. In between these... 

Flybertsen M S and Louie S G 1985 First-principles theory of quasiparticles Calculation of band gaps in semiconductors and insulators Phys. Rev. Lett. 55 1418... 

Campillo I, Silkin V M, Pitarke J M, Chulkov E V, Rubio A and Echenique P M 2000 First-principles calculations of hot-electron lifetimes in metals Phys. Rev. B 61 13 484-92... 

Stampfl C, van de Walle C G, Vogel D, Kruger P and Pollmann J 2000 Native defects and impurities in InN First-principles studies using the local-density approximation and self-interaction and relaxation-corrected pseudopotentials Phys. Rev. B 61 R7846-9... 

Anisimov V I, Kuiper P and Nordgren J 1994 First-principles calculation of NIG valence spectra in the impurity-Anderson-model approximation Phys. Rev. B 50 8257-65... 

Anisimov V I, Aryasetiawan F and Liechtenstein A I 1997 First-principles calculations of the electronic structure and spectra of strongly correlated systems The LDA+U method J. Phys. Condens Matters 767... 

Podloucky R, Zeller R and Dederichs P H 1980 Electronic structure of magnetic Impurities calculated from first principles Phys. Rev. B 22 5777... 

SmarglassI E and Madden P A 1994 Orbital-free kinetic-energy functionals for first-principles molecular dynamics Phys. Rev. B 49 5220-6... 

Watson S C and Carter E A 2000 Linear-scaling parallel algorithms for the first principles treatment of metals Comp. Pbys. Common. 128 67-92... 

Figure B3.3.12. Sulphur atoms in liquid iron at the Earth s core conditions, simnlated by first-principle Car-Parrinello molecular dynamics, (a) Initial conditions, showing a mannally-prepared initial cluster of snlphur atoms, (b) A short tune later, indicating spontaneous dispersal of the snlphur atoms, which mingle with the surroundmg iron atoms. Thanks are dne to D Alfe and M J Gillan for this figure. For fiirtlier details see [210. 211].

Gain G and Pasquarello A 1993 First-principles molecular dynamics Computer Simulation in Chemioal Physios vol 397 NATO ASI Series C ed M P Allen and D J Tildesley (Dordrecht Kluwer) pp 261-313... 

Car R 1996 Molecular dynamics from first principles Monte Carlo and Moleoular Dynamios of Condensed Matter Systems vo 49 ed K Binder and G Ciccotti (Bologna Italian Physical Society) pp 601-34... 

Alfe D and Gillan M J 1998 First-principles simulations of liquid Fe-S under Earth s core conditions Phys. Rev. B 58 8248-56... 

Espanol P 1996 Dissipative particle dynamics for a harmonic chain a first-principles derivation Phys. Rev. B 53 1572... 

Weakliem P C, Wu C J and Carter E A 1992 First-principles-derived dynamics of a surface reaction fluorine etching of Si(IOO) Phys. Rev. Lett. 69 200-3... 

Carter L E, Khodabandeh S, Weakliem P C and Carter E A 1994 First-principles-derived dynamics of Fj reactive scattering on Si(100)-2 x 1 j. Chem Phys. 100 2277-88... 

In this chapter, we discussed the significance of the GP effect in chemical reactions, that is, the influence of the upper electronic state(s) on the reactive and nonreactive transition probabilities of the ground adiabatic state. In order to include this effect, the ordinary BO equations are extended either by using a HLH phase or by deriving them from first principles. Considering the HLH phase due to the presence of a conical intersection between the ground and the first excited state, the general fomi of the vector potential, hence the effective... 

L, Salem, Electrons in Chemical Reactions First Principles, John Wiley Sons, Inc., New York, 1982. 

Absolute Binding Constants from First Principles ... 

The problems that occur when one tries to estimate affinity in terms of component terms do not arise when perturbation methods are used with simulations in order to compute potentials of mean force or free energies for molecular transformations simulations use a simple physical force field and thereby implicitly include all component terms discussed earlier. We have used the molecular transformation approach to compute binding affinities from these first principles [14]. The basic approach had been introduced in early work, in which we studied the affinity of xenon for myoglobin [11]. The procedure was to gradually decrease the interactions between xenon atom and protein, and compute the free energy change by standard perturbation methods, cf. (10). An (issential component is to impose a restraint on the... 

E. M. Boczko and C. L. Brooks III. First principles calculation of the folding free energy of a three helix bundle protein. Science, 269 393-396, 1995. 

Abstract. This paper presents results from quantum molecular dynamics Simula tions applied to catalytic reactions, focusing on ethylene polymerization by metallocene catalysts. The entire reaction path could be monitored, showing the full molecular dynamics of the reaction. Detailed information on, e.g., the importance of the so-called agostic interaction could be obtained. Also presented are results of static simulations of the Car-Parrinello type, applied to orthorhombic crystalline polyethylene. These simulations for the first time led to a first principles value for the ultimate Young s modulus of a synthetic polymer with demonstrated basis set convergence, taking into account the full three-dimensional structure of the crystal. 

All three tasks are generally too complicated to be solved from first principles. They are, therefore, tackled by making use of prior information, and of information that has been condensed into knowledge. The amount of information that has to be processed is often quite large. At present, more than 41 million different compounds are known all have a series of properties, physical, chemical, or biological all can be made in many different ways, by a wide range of reactions all can be characterized by a host of spectra. This immense amount of information can be processed only by electronic means, by the power of the computer. 

Mujica A and R J Needs 1993. First-principles Calculations of the Structural Properties, Stability, aind Band Structure of Complex Tetrahedral Phases of Germanium ST12 and BC8. Physical Review B48 17010-17017. 

Needs R J and Mujica 1995. First-principles Pseudopotential Study of the Structural Phases of Silicon. Physical Review B51 9652-9660. 

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