Questions tagged [quantum-chemistry]
For questions about quantum chemistry.
37
questions
9
votes
1answer
88 views
Energy decomposition analysis (EDA) at transition state
I am trying to understand the interaction between the nucleophile and the substrate for some SN2 reactions (e.g. $\ce{I- +CH3Cl->CH3I + Cl-}$) at the transition states. Now, it seems that EDA would ...
10
votes
1answer
92 views
What are the trade-offs setting DIRSCF to either .TRUE. or .FALSE. (the default) in GAMESS (US)?
The first software I used to run calculations was Gaussian09. When submitting a input, I used to see a pattern of resource usage where the allocated CPU quickly maxed out, remaining high most of the ...
10
votes
1answer
58 views
How to understand the formation of covalent bond from the viewpoint of wavefunction interaction?
The formation of the covalent bond is usually understood from the electron sharing, like explained by the following figure:
However, this simple physical picture seemingly hinders many things. In ...
10
votes
3answers
1k views
What does “level of theory” mean?
I was reading this paper on the QM9 synthetic molecular database and their computed properties. It is stated that
All properties were calculated at the B3LYP/6-31G(2df,p) level of
quantum chemistry.
...
10
votes
1answer
249 views
Does One-to-One Correspondence of Hohenberg Kohn Theorem Mean Bijective or Injective and How to Prove it?
I have asked a similar question but after thinking about it I have a more specific question.
According to Ullrich, Carsten A.. Time-Dependent Density-Functional Theory : Concepts and Applications, the ...
15
votes
2answers
51 views
What is the difference between orbital localisation and NBO?
I am new to computational chemistry, I have used mainly GAMESS and Orca. In GAMESS, there are orbital localisation schemes like Pipek-Mezey, Ruedenberg-Edminston, etc. which generate orbitals that ...
16
votes
1answer
993 views
Does the Schrödinger equation have unique solutions?
I am learning DFT and the Hohenberg Kohn Theorem of Existence. It says that there is a one-to-one correspondence between the external potential and the density.
However the proofs that I have seen ...
8
votes
0answers
61 views
How to interpret second order perturbation theory analysis from NBO calculations?
The question is quite simple — how to interpret NBO results of second order perturbation theory analysis? As I have read several papers the most important interactions are $\pi\rightarrow\pi^{*}$, $LP\...
12
votes
1answer
171 views
How to explain Density Functional Theory results to an experimentalist?
When we present our Density Functional Theory simulation results e.g. lattice parameters, stacking fault energies, band gaps, etc. to people who are experimentalists then the very first question ...
9
votes
1answer
358 views
High precision helium energy
In the paper "High Precision Theory of Atomic Helium", Drake lists the then best-known ground state energy of the Schrödinger equation for helium to 22 digits as:
$$\lambda_0 \approx -2....
9
votes
1answer
40 views
How can I determine the maximum value of a spin orbital and its derivative in any direction?
I'd like to be able to recover the maximum value that any of the basis functions can take, as well as their maximum derivative. How can I do this?
For context, I need it because I want to calculate ...
9
votes
2answers
63 views
Analytic Hessians for meta-GGA functionals
In many of the free/open-source QM programs like GAMESS, ORCA, NWChem, the calculation of analytic hessians is not possible when a meta-GGA density functional is used, like M06-2X. My first question ...
10
votes
2answers
214 views
Normalization constant and Roothaan Equations
Roothaan Hall Equations:
The Hartree-Fock equations are a set of modified Schrodinger equations:
$f_{i}\psi_{m}=\epsilon_{m}\psi_{m}$
where:
The Fock operator ($f_{i}$) is given by (restricted case):
...
8
votes
1answer
171 views
How to fix Error Link9999 in Gaussian
I have a problem with geometry optimization in Gaussian software with M062X method. The structure was smoothly optimized using M062X/Gen. Nevertheless, I need very accurate results so afterwards the ...
5
votes
1answer
86 views
What are the other matrix elements in singlet symmetry-adapted CISD?
Szabo/Ostlund list the CI matrix elements between singlet symmetry-adapted configurations (SAC) in Table 4.1 of their book:
$$
\langle ^1\Psi^r_ a \lvert \mathcal{H} - E_ 0 \rvert ^1\Psi^r_ a \rangle,
...
15
votes
3answers
119 views
Candidate structures for global minimum determination
What are the best packages that can generate candidate structures for quantum chemical optimization (DFT or CCSD) to find the global minimum? I am working on the gas-phase small inorganic clusters (...
8
votes
1answer
103 views
Is this G16 molecular hyperpolarizability error reproducible in other software?
I was trying to calculate the hyperpolarizability $\beta$ of a cluster of two water molecules in Gaussian16 using the route card:
...
9
votes
1answer
67 views
What are some good ways to model radicals and similar intermediates of reactions
Calculations in the ground electronic state are probably the simplest cases where defaults in terms of charge (typically zero) and spin (singlet) are chosen by the calculation software. However, when ...
6
votes
1answer
83 views
I get an error 'Conversion from Z-matrix to cartesian coordinates failed' in Gaussian09. Any suggestions?
I'm doing my calculations using G09W. My OS is Windows 7 (64-bit). This error occurs in the frequency calculation. What's even weirder is that it seems to happen right after everything is already ...
6
votes
1answer
55 views
I get this error in Gaussian09 even though I have enough memory. “Error termination in NtrErr: NtrErr called from FIOCnC.” Any suggestions?
Whenever read-write files get to about 20Gb, I get this error. I know that, in G09, one rw file is limited to 16Gb. So I have set the software to write several RWFs. But it still keeps producing this ...
10
votes
1answer
77 views
Regarding oscillatory strength theoretical units to experimental ones
The output of Gaussian rotatory and oscillatory strength intensities, plus a gaussian/lorentzian fit, translates to a theoretical CD/UV-vis spectra.
In order to try and compare with experimental ...
9
votes
1answer
46 views
Is there an anisotropy factor (g factor) for TDDFT absorption and circular dichroism calculations?
Experimentally, anisotropy factor is calculated by dividing the CD (circular dichroism) spectra by the absorbance spectra and multiplying by a factor of 32980 (in order to get a dimensionless quantity)...
7
votes
1answer
76 views
Bond Order: When and how is it used today?
We all learned about single vs double vs triple bonds in high school chemistry and biology. We learned that unsaturated fats have double bonds whereas saturated fats have only single bonds, which ...
5
votes
1answer
104 views
How is MCTDH derived?
In the multi-configurational time-dependent Hartree (MCTDH) method, the equation of motion is derived from the time-dependent Schrödinger equation by substituting the wavefunction ansatz expanded in a ...
13
votes
2answers
134 views
A CCSD(T) geometry optimization in Gaussian09 is deviating too far from the minimum. How do I deal with it?
I am doing a CCSD(T) geometry optimization on a series of molecules. One of the geometry optimizations took about 2 weeks even though an analogous molecule with the same number of basis functions took ...
32
votes
1answer
1k views
Was Walter Kohn wrong about this?
In Kohn's Nobel Lecture, he claimed that:
"In general the many-electron wave function $\Psi(\mathbf{r}_1,\ldots,\mathbf{r}_N)$ for a system of $N$ electrons is not a legitimate scientific concept,...
16
votes
4answers
322 views
Is there a set of updated, comprehensive benchmarks for speed comparison between different quantum chemistry packages?
I've found a page dedicated to quantum chemistry packages benchmarks, on GitHub, qmspeedtest. But most results there are several years old, and so probably outdated. Is there some place where we can ...
12
votes
2answers
348 views
Total spin and/or multiplicity for transition metal ions?
I am trying to input various charge states of various transition metal ion species into DFT calculations. The program requires an input of multiplicity = 2*(total spin) + 1.
I have an undergraduate-...
8
votes
1answer
99 views
The correlation energy from frozen natural orbtials (FNOs) using CCSD and MPBT(2)?
In other works and from the paper: Scaling Up Electronic Structure Calculations on Quantum Computers: The Frozen Natural Orbital Based Method of Increments.
I have seen that the corrected CCSD ...
15
votes
2answers
328 views
Materials Modeling with Raspberry Pi?
Does anyone have any knowledge or direction for creating a homemade Beowolf cluster for materials modeling?I would like to be able to run my own "hobby" simulations at home, so a low energy, ...
13
votes
2answers
377 views
Since MKL is not optimized for AMD hardware, should I use a math library specific to AMD, or would an open-source one be just as good?
The codes for quantum mechanical calculations make heavy use of linear algebra, and it seems most of them delegate this task to time-tested and highly optimized libraries, instead of trying to deploy ...
24
votes
2answers
2k views
What are the “smart algorithms” applied to solve the “curse of dimensionality”?
The "curse of dimensionality" is an ubiquitous issue arising in both electronic structure and quantum molecular dynamics, which refers to the exponential scaling of computational cost with ...
19
votes
2answers
305 views
What significant matter modelling methods are implemented in commercial software, for which there is no freeware alternative?
There is an ever-growing list of freeware and open-source software for solid-state physics and quantum chemistry.
But many commercial programs still thrive, even in 2020, and their cost can be in ...
22
votes
5answers
365 views
When and Why does Density Functional Theory (DFT) fail?
Every method has its strengths and weaknesses. For instance, a strength of DFT is that is has HF like speeds, but can also account for electron-correlation and this is a pretty big feature since ...
20
votes
3answers
140 views
How can quantum computing accelerate materials modeling?
Materials modeling is very computationally intensive and first-principles simulation of a real system of reasonable size typically involves the use of classical supercomputers.
How can quantum ...
13
votes
1answer
66 views
In which situations/problems, does one need to employ the nonorthogonal configuration interaction method?
Nonorthogonal configuration interaction is known to be a computationally inefficient approach. Recently, there has been a number of developments that have been done to improve the efficiency of ...
25
votes
1answer
313 views
Approximate equivalence table between Pople's basis sets and Jensen's DFT optimized polarization consistent basis sets (pcseg-n)
At first I posted this question in chemistry.stackexchange.com, before materials.stackexchange.com was launched in beta. As it went unaswered, I'm giving a try here.
I have some calculations results ...
