Questions tagged [ab-initio]

For questions relating to quantum chemistry using wavefunction-based methods and solving the Schrödinger equation.

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What are the steps of Hartree-Fock Theory?

Outline the steps involved in the Hartree–Fock method for the calculation of molecular electronic structure. I understand the basics of HF, in that it does not account for electron correlation (...
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38 views

Calculating the Molecular Orbitals of a Molecular State [closed]

I am performing ab initio calculations on a heteronuclear diatomic compound using the MRCI method on the MOLPRO quantum chemistry package. I obtained the molecular states of the compound but I was ...
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1answer
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Ab Initio and Molecular Orbitals [closed]

What is the difference between ab initio calculations and molecular orbital theory?
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30 views

Guide to DFT functionals [duplicate]

Having recently begun studying Quantum and computational chemistry in depth... I am looking for a manual, text, or guide of any form that could explain the basic formulations and potential of the ...
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2answers
145 views

Spectroscopic constants - explanation

I'm a beginner in spectroscopy and I have troubles understanding papers describing values of spectroscopic constants. This paper, for example, describes constants $T_e, R_e, \omega_e, \omega_ex_e, B_e,...
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135 views

How to evaluate the expectation value of the Hamiltonian for a three electron Slater determinant?

I'm having trouble with a few concepts dealing with slater determinants and many electron systems. In particular, when dealing with 3 electron systems, I know that $$ \psi_0 = \frac{1}{\sqrt{6}} \det ...
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31 views

tolerable error, CASSCF simulation of UV/Vis spectrum

Please forgive my ignorance of experimental spectroscopy. I am a computational chemist, not an experimental one. My question is: what would be considered a tolerable or reasonable difference between ...
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36 views

How to use potential energy surface represented by a neural network for molecular dynamics simulation?

I trained a neural network that represents the potential energy surface of a periodic system consists of $50$ atoms. The neural network takes the structure proposed by Behler and Parrinello in 2007. ...
2
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27 views

GVP(PP) orbital energies?

Hartree-Fock orbital energies can be interpreted physically, e.g. in Koopmans theorem, while one cannot assign active MCSCF orbitals to energies in general. What about GVB, say for example GVB(PP) ...
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1answer
69 views

Why is the active space for the dinitrogen cation defined this large in my example?

I have a Molpro script which computes $\ce{N2^+}$ potential energies. The significant part is the input for the wave function: ...
7
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1answer
356 views

Why is Coupled Cluster not variational?

It has been noted in several sources (e.g. J. Romero et al. Strategies for quantum computing molecular energies using the unitary coupled cluster ansatz. arXiv:1701.02691 [quant-ph]) that one of the ...
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79 views

Bond order analysis in molpro

I'm trying to compute bond orders in a molecule, let's consider S2 as an example. I'm not entirely sure what's the right way to do that, but I assume NBO (Natural Bond Orbital) should give me what I ...
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247 views

What all computing knowledge should a computational chemist traditionally have? [closed]

If I want to develop algorithms or computer programs for studying chemical systems, where should I start? Is learning one or two programming languages like FORTRAN enough? And if I do it, then how do ...
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Can someone suggest me important references for deriving EOM in MCSCF?

I am currently starting a project dealing with MCSCF method. Can someone please give me references (papers or lecture notes are preferred) which may be considered as the "corner stones" in the history ...
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3answers
175 views

How closely should the energy components of ab initio SCF results at a stationary nuclear configuration preserve the virial theorem?

When running a SCF geometry optimization for water molecule, I found that the energy components of the optimized geometrical structure appear to deviate from Virial theorem sightly: Kinetic energy = ...
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2answers
94 views

Potential energy surface when spin changes

I'm trying to compute potential energy surface of S4 molecule (in MOLPRO 2015) along S2-S2 bond (it has a trapezoidal shape) from equilibrium to the dissociation threshold, all the other coordinates ...
10
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2answers
739 views

Proof of Brillouin's theorem using the diagonality of the Fock matrix

I'm working my way through Szabo and Ostlund's Modern Quantum Chemistry. I am having trouble understanding the proof and significance of Brillouin's theorem. According to the book: Now, by ...
8
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1answer
117 views

What's a good measure of the Eigen-ness of a wavefunction?

Just wondering if someone can recommend an easy-to-compute measure for the Eigen-ness of a wave function, such as the wave functions computed using ab initio method? For a wave function solved using ...
12
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2answers
847 views

How does optimizing the molecular orbital coefficients in CASSCF improve its multi-reference capabilties?

The complete active space self-consistent field (CASSCF) method is a special kind of multi-configurational SCF procedure, attempting to combine Hartree-Fock (HF) and configuration interaction (CI). In ...
13
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4answers
843 views

Is coupled cluster variational for two electrons?

I know that coupled cluster (CC) is not variational for the general case. However, if we only have two electrons with one nucleus, CCSD should be exact for this system like full configuration ...
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1answer
58 views

Building a solid-liquid interface

I am trying to build a solid-liquid interface to be simulate using molecular dynamics. Since, I would be using ab initio molecular dynamics (cpmd or cp2k), I need the minimum cell dimensions. Please ...
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52 views

Paper Data Replication

I read a paper recently - Here. I found the concept of Electride materials very interesting and wanted to mess around with them myself. I tried to replicate the partial electron density plots shown in ...
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2answers
1k views

Why are correlation consistent basis sets used with DFT calculations?

Reading some papers, there is a bit of a curious observation that does not exactly make a lot of sense to me. In Quantum Chemistry, different methods exist to carry out geometry optimisation and ...
15
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2answers
2k views

What are typical runtimes for CASSCF calculations?

I'm doing single point energy calculations of FeS using ORCA. I originally used DFT with a variety of functionals, and these calculations all took less than a minute. Now I'm attempting to run CASSCF ...
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1answer
205 views

Ab initio effective potentials

I have been reading a journal article on ab-initio pseudo-potentials, and I need some help understanding it. The article is C. F. Melius and W. A. Goddard, III. Phys. Rev. A 1974, 10, 1528. A summary ...
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1answer
1k views

How to choose the best method and basis set for a calculation in computational chemistry?

In Quantum chemical calculations, it is not always the case that the more complex (correlated) the method or the basis set the more accurate the results. For example, it's sometimes found that MP2 ...
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1answer
1k views

Initial guess for Unrestricted Hartree-Fock calculation

I am implementing an Unrestricted Hartree-Fock (UHF) calculation, following Ref. [1]. It works fine for a odd number of electrons ($N_\alpha\neq N_\beta$) since, despite the same initial guess for $\...
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2answers
836 views

Gaussian09 vs home made Hartree-Fock implementation

I implemented a restricted Hartree-Fock (RHF) calculation in the STO-3G basis set, as described in Szabo and Ostlund's book [1]. I managed to reproduce the energies of all their calculations ($\ce{H_2}...
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3answers
2k views

Boys function for Gaussian integrals in ab-initio calculations

A few days ago I mentioned a problem with an Hartree-Fock program I am writing (HF using cartesian Pople's STO-3G basis set). I can reproduce overlap and kinetic integrals of some references for ($\ce{...
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1answer
139 views

How does one calculate chemical shift in a gauge independent manner?

The literature on ab initio calculations of chemical shift in NMR experiments usually provide Lamb's and Ramsey's formulae as the solution. Yet the expressions explicitly depend on vector potential ...
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3answers
2k views

Computing two-electron integrals with an STO-3G basis set

I am trying to implement a restricted Hartree-Fock calculation using an STO-3G basis set, for fun. I managed to perform this calculation where only $\mathrm{1s}$ orbitals are present ($\ce{H2}$ and $\...
26
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2answers
8k views

Is density functional theory an ab initio method?

The following comment by Wildcat made me think about whether density functional theory (DFT) can be considered an ab initio method. @Martin-マーチン, this is sort of nitpicking, but DFT (where the last ...