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Questions tagged [density-functional-theory]

Density functional theory (DFT) is a quantum mechanical model used to estimate the electronic structure of molecules and condensed matter. In broad terms, DFT works by treating all the electrons in the system as a single electron density, and computing physical quantities of interest as functionals of that electron density. (from Physics.SE)

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Striking examples where Kohn-Sham orbitals clearly have no physical meaning

In Density Functional Theory courses, one is often reminded that Kohn-Sham orbitals are often said to bear no any physical meaning. They only represent a noninteracting reference system which has the ...
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d-orbital splittings in WS2 monolayer

The formerly degenerate $d$ orbitals of the tungsten atoms in the $\ce{WS2}$ monolayer are split into three groups: (1) $\mathrm{d}_{z^2}$, (2) $\mathrm{d}_{x^2-y^2}, \mathrm{d}_{xy}$ and (3) $\mathrm{...
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DFT Functional Selection Criteria

I have a very very general question: In DFT functional selection , mostly people speak about the most recent ones. For example my professor always asks: " which DFT Functional did you select ? " ...
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How do Quantum Software Packages Work?

If one wants to calculate a moderate size Alkane (with say 10-15 Carbons , assuming 100 electrons , with Restricted Hartree Fock based methods) we can simply say that electron-electron part will be $...
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Suggest methods and basis sets for a variety of systems

Please help me with any/all of the cases below. In the following cases, the named method and basis set are not suitable for the chemical systems. Why aren't they? Could you suggest a suitable method/...
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Equivalent of Szabo and Ostlund book for DFT

Szabo and Ostlund book Modern quantum chemistry [1] is extremely useful to understand Hartree-Fock and post-Hartree-Fock methods. Not only it explains the theory behind such methods, but it is also ...
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How should I go about picking a functional for DFT calculations?

I've been looking to use time-dependent density functional theory, but reading the literature I keep getting overwhelmed by how many different functionals there are. How should I go about selecting ...
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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 ...
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What's the difference between PBE and B3LYP methods?

I can't find an answer to that question. I was told that in B3LYP, more variables implemented in the method are empirical, but I can't find anywhere if it's true, and I'm sure it's not the only ...
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DFT Code for Atoms : Sources

Some time ago I implemented the restricted and unrestricted Hartree-Fock methods. I had a lot of fun and I learned a lot. It goes without saying that Szabo and Ostlund's book "Modern Quantum Chemistry"...
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Do modern dispersion-corrected DFT methods give more accurate molecular geometries?

I was discussing with a colleague the use of modern dispersion-corrected density functionals. I take it almost as a given that the methods generally produce "better" (for some definition) geometries, ...
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Interpretation of TD-DFT results

For the first time I'm doing TD-DFT calculations (wB97XD functional) in Gaussian 09 for an open-shell system and the results look like the hell of a mess for me. The molecule is rather big, so I ...
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Are there any full worked examples of DFT calculations?

I just started learning DFT and now I am totally confused. Assuming I want to use B3LYP: \begin{align} v_s\left(\textbf{r}\right) &= v_\text{ext}\left(\textbf{r}\right) + \int d^3r\frac{n\left( \...
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How to define custom force in quantum chemistry packages?

I don't know if this is really applicable but I want to add a custom force (say, $F(x,y,z)$) to some atoms in my geometry optimization. Is there any way to add such forces to the DFT or molecular ...
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Determining Kohn-Sham and Hartree Fock virtual orbitals: The underlying field

In Frank Jensen Introduction to Computational Chemistry from 2007, I stumbled upon this paragraph about whether to assign meaning to the KS orbitals or not Another difference is that the unoccupied ...
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What to do with (large) imaginary frequencies for constrained minimum structures?

I am performing DFT calculations using ORCA 4.0.1 on an enzyme active site model. The model contains 89 atoms including the substrate (see Animation 1), five of which are fixed in space (the spherical ...
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Why is Density Functional Theory notoriously bad at describing oxygen molecules?

I read in several papers that DFT is notoriously bad at describing free oxygen molecules but in none of them an explanation or reference concerning the problem has been provided. I guess this has ...
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What do short-range and long-range corrections mean in DFT methods?

Currently I am looking for the most accurate calculation method for a simple non-conjugate molecule consist of C, N, O and H. Normally I would try each method for a similar and known molecule then ...
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Can PBE (and LDA) actually be a better choice sometimes?

Part of my work as an inorganic chemist is to investigate the magnetic coupling between metallic centers in coordination compounds. After some time, I've noticed that the classic PBE functional is the ...
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How to simulate chemical reactions in GAMESS?

I am rather newb in GAMESS field but finally, learned to make input files for most molecular simulations and could even use TD-DFT for excited states (special thanks to Geoff Hutchison for his help). ...
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Better functionals to work with transition metals

My Masters in inorganic chemistry is focused in magnetic properties of transition metals; great part of the work is done with DFT methods using softwares like ORCA and NWChem, but since my University ...
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When is it necessary to check wavefunction stability in density functional theory?

In Gaussian, there is a stable keyword that checks the stability of the wavefunction. Using stable=opt reoptimizes the ...
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Estimating stability and mean life of anomalous tautomers

A pair of bases in the DNA, say, A-T, have a tautomerized form A*-T* (resulting from switching the sides of both protons along the hydrogen bridges). I have studied how, by means of DFT computations, ...
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Density Functional Theory with Generalized Gradient Approxmations (GGA) - What Happens if the Electron Density Shows a “Kink” at the Ion Position?

My question may be stupid, so please correct me if you find anything which is obviously erroneous. In the following I will place a question mark (?) besides points/steps I consider doubtful. My ...
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PBE vs. PBEPBE functional

I've found good explanation what the PBE functional is. However, sometimes I see PBEPBE and I cannot find any good information about what this means and how it's different from PBE. The Gaussian ...
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Defining and testing custom made DFT functionals?

What is a good and free software for this endeavor? Any recommended articles on the subject? I want to design dft functionals, trying out different parametrizations and optimizing mixing constants for ...
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How DFT-D3 incorporates coordination number (CN) into C6

I'm reading Grimme's DFT-D3 paper but really puzzled by how the $\mathrm{CN}$ is considered in the calculation of $C_\mathrm{6}$ coefficients. (Stefan Grimme, Jens Antony, Stephan Ehrlich, and Helge ...
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How does one actually get the energy from the Kohn–Sham equations?

This might be a silly question, but how does one acquire the energy of the system from the Kohn–Sham equations? $\left[ -\frac{1}{2}\nabla^2 + V_{eN}(\vec{r}) + V_{ee}(\vec{r}) + V_{xc}(\vec{r}) \...
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Exchange-correlation hole

I did a google and chemistry.exchange search and found several technical definitions of the exchange correlation hole. The questions that I want to proposes are: What the exchange-correlation hole ...
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Use of basis set in DFT (Density Functional Theory)

Basis sets are used to guess the electronic wave functions for Hartree Fock or similar methods, which are quite legitimate since these methods deal with the wave function of each and every electron. ...
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Strange “far out” orbitals in HF and DFT calculations. Why do they occur?

I calculated some orbitals and I get quite strange results with orbital geometries I wouldn't expect from MO theory. A more experienced colleague just said: "That's always the case with big basis sets,...
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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 ...
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There are no wavefunctions in DFT

I have seen this phrase several times across DFT textbooks. However, I am not sure if it still holds. Was there a change or a theorem that proved it otherwise? Several programs display wavefunctions ...
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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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Difference between single point energy and dimerization energy

I am investigating potential energy surface characteristics of some electrostatic monomeric interactions e.g. $\ce{F-H}$...$\ce{F-H}$. I'm using DFT and SCS-MP2 to perform the necessary calculations ...
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Is there proof that the exact exchange correlation functional is an analytic function?

Mathematics show that some problems cannot be solved analytically. Could this be true for the exact exchange correlation functional? Most textbooks state that the form of the exact exchange ...
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Calculating dipole moments from atomic partial charges

How can I calculate dipole moment of a complex molecule where the partial charges are available from density functional theory? I have the coordinates of each atom from atomistic simulations of an ...
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Hartree product and the Slater determinant

I am very new to theoretical chemistry so my question may sound very basic to most. It is known that the Hartree product does not satisfy the antisymmetry principle for electrons while the Slater ...
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Excited-states properties with traditional density functional theory

Recently I was shown the book "Density Functional Theory II, Relativistic and Time Dependent Extensions" by Nalewajski in which a chapter from E. K. U. Gross et al. is printed. [1] This chapter ...
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Calculating singlet-triplet gap and open-shell singlet character

I am trying to calculate the singlet-triplet energy gap ($S_0-T_1$) of a conjugated system (18 atoms). For the singlet $S_0$ state, assumed to be closed shell, the Gaussian options were ...
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Why do we integrate square of wave function over N-1 electron coordinates?

Quote form F.Jensen's Introduction to computational chemistry: "The electron density is the square of the wavefunction, integrated over N-1 electron coordinates..." Why do we integrate over N-1 ...
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B3LYP Explained

In my inorganic chemistry class, we were introduced to computational chemistry. We are told to use B3LYP theory in the program, but we never actually learned any of the computation yet. Could anyone ...
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Is there a reliable way to determine if a chemical system is more suited to be calculated using a multireference method instead of DFT?

Some time ago I recall hearing a professor say that looking at a DFT result (I don't remember exactly what, a TD-DFT, spin contamination etc...), he could tell that the system was multireferenced. My ...
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Why does the local density approximation (LDA) overestimate atomization energy?

I have read numerous times that the local density approximation (LDA) overestimates atomization energy. For example, here is a quote from Dr. Burke's book: LDA typically overbinds molecules by ...
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A thorough benchmark of DFT functionals without dispersion corrections

So, I'm looking for a benchmark of DFT functionals not including dispersion corrections. Something similar to Grimme's and coworkers GMTKN30 database, but for benchmark calculations done without ...
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Computing of strengthening of π-interaction

I need some practical advise. What would be the easiest approach to compute strengthening or weakening of π-interaction in a bond with multipole-bond character. I'm not really fond of going through ...
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Ground state oxidation potential and Ionization potential from density functional theory (DFT)

Can someone please tell me how to calculate the ground state oxidation potential (GSOP)? I understand that according to Koopmans' theorem, the negative of HOMO can be considered as the GSOP. Is there ...
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Are there other Density Functional Theories other than Kohn Sham DFT?

For some reason I thought that the term DFT and Kohn Sham DFT were interchangeable. Kohn Sham DFT is certainly one of the most popular. But are there other types of DFT that are in use today? I have ...
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Calculation of rate constant for bimolecular reaction from Gaussian DFT calculations

I am working with a bimolecular reaction for which I have computed the energy profile. I have output files for TS and reactants which I intend to use for rate constant calculations. From TST we have: ...
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How to define the initial guess for the electron density?

This is a technical question. If I have a one-dimensional box of length L, and an electron density existing in the box and integrating to N electrons. And if I want to determine the electron density ...