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Questions tagged [theoretical-chemistry]

For questions seeking answers deduced from or composed of theories regarding the chemical substances and about models and methods of theoretical chemistry.

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0answers
37 views

Convergence failure [on hold]

I trying to run a DFT calculation with the following job input: aui2s2pc20h18 0 1 # PBEPBE/LANL2DZ Opt Freq NoSymm aui2s2pc20h18 0 1 Au 2.9788534146 ...
1
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0answers
54 views

Hartree Fock for an atom (Beryllium)?

I'm working on solution of Hartree-Fock equation for Beryllium in configuration $1s^2 2s^2$, expanding the orbital with STO-3G basis $$\phi_k=\sum_{p=0}^3 C_{kp}e^{-\alpha_{kp}r^2}$$ I know the values ...
1
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2answers
42 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,...
7
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0answers
53 views

Why does the exchange interaction in Hartree-Fock theory lower the total energy?

In Hartree-Fock theory, the expectation value of the total energy can be written as $$E = \langle\Psi| H |\Psi\rangle = \sum_{a} \langle a| h |a \rangle + \frac{1}{2}\sum_{ab} \big( [aa |bb] - [ab|ba]...
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1answer
31 views

Charge, multiplicity, level of theory and coordination coordinates of gold compleaxes [closed]

Good day, I need to learn a trick in answering the following questions: How to come up with cartesian coordinates of a complex say, [Au(CH2)2(S)PPh2]2, to be ran on Gaussian? The charge and its ...
1
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1answer
30 views

Number of stable molecules of artificial molecule XY4 [closed]

Suppose element X has $5$ stable isotopes, and element Y has $6$ stable isotopes. Find the number of natural molecules, knowing that an X has a charge of $+4$ and Y has a charge of $-1$. What I tried ...
7
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1answer
118 views

What is the difference between a configuration state function and a Slater determinant?

I do not understand the distinction between configuration state functions and Slater determinants. Is not every Slater determinant a CSF ? Please explain the difference and the use/need of ...
1
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2answers
66 views

Dissociation degree hell, Ostwald's law of dilution

Greetings dear chemists! I got a nice exam problem on wich i am stuck for hours, well maybe the problem is with me. I know the problem can be solved. So here we go. We got a weak monoprotic acid, we ...
2
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0answers
28 views

What is the ANO-RCC basis set and how does it work?

On the basis set exchange, the ANO-RCC basis looks huge, even for hydrogen: ...
2
votes
1answer
29 views

A theoretical framework for the formalization of chemical interaction and configuration based properties

Is there an attempt in any area of chemistry to formalize the way a molecule's properties change based on its configuration and the resulting changes in interaction with other molecules. For example, ...
1
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0answers
36 views

GAMESS Gaussian qst2 method alternative

I've heard about the qst2 Gaussian method but I don't have any licence so I use the free GAMESS-US. Nevertheless, I didn't find any Gamess method which allows a TS finding like qst2. Have you heard ...
5
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2answers
54 views

Intuition for why catalyst affects both forward and reverse reactions equally?

I have looked for quite a long time on the site however all the answers involve mathematical explanations involving Arrhenius's equation. I would really like an intuitive reason (or one using ...
9
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0answers
163 views

What is the largest coupled cluster calculation that has ever been done (as of March 2019)?

I am doing some research and trying to make sure the numbers I am reporting are accurate. I found that the paper by Sylvetsky et. al. says:[1] We were, however, able to complete a ...
7
votes
1answer
239 views

Pauli exclusion principle

Pauli exclusion principle states that 'No two electron can exist in same state' or 'No two electron can have same set of quantum numbers'. But in reality there is no state of electron. The state is ...
2
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2answers
113 views

Ab initio calculations

Why are quantum mechanical calculations so computationally expensive? What exactly is the process that makes it so time taking?
2
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0answers
75 views

Good software/module in python to determine nuclear attraction integral in Slater type orbital basis sets

I am trying to solve a Hamiltonian of one electron and 10 stationary nuclear centers. here, the electron is treated quantum mechanically and nuclear centers are treated classically objects. The ...
6
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0answers
84 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 ...
0
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0answers
21 views

Why do identical protons not couple with each other in 1H NMR? [duplicate]

So basically I'm wondering why the different protons in ...let's say trans-stilbene do not couple with each other. I'm aware of the fact that they are chemically and magnetically equivalent. They ...
1
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2answers
78 views

Concept of enthalpy at a given temperature

In thermodynamics, we always quote a fixed temperature, whenever we mention enthalpy of a reaction. For instance, one can determine the enthalpy of combustion of methane at 25 °C. Now almost all ...
9
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2answers
134 views

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,...
1
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1answer
86 views

Simulation of Miller-Urey experience [closed]

The Miller-Urey experiment shows that it easy in a primordial atmosphere similar to early earth to generate amino acids,my question: is it theoretically possible to simulate this experience on any ...
5
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1answer
87 views

Conformer generation for radicals

Is there an automatic way to generate conformers for radical like systems (spin multiplicity is doublet)? My system for the study is a substituted fullerene with a missing H atom from the functional ...
5
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1answer
51 views

Is the neutral di-µ-oxo-bridged manganese dimer with eight ammonia ligands a reasonable structure?

In its guide to model antiferromagnetic couplig, Gaussian uses $\ce{Mn2O2(NH3)8}$ as a model compound.[1] It argues that manganese is in II oxidation high spin state; in other words, in both manganese ...
5
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1answer
44 views

What determines the coefficients in the wavefunction of a hybrid orbital?

I was studying the hybridization of carbon atoms and I came to figure out that the $sp$ hybridization wavefunction is given as $$|sp_{+}\rangle =\frac{1}{\sqrt{2}}\left(\psi_{2s}+\psi_{2p_x}\right)$$ ...
11
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1answer
387 views

Is phosphorine (C₅H₅P) aromatic?

Phophorine seems aromatic as it has 6 conjugated electrons. But the answer given is that it is not. This seems odd since pyridine has a similar structure and is also aromatic. Thus I ask is ...
7
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0answers
76 views

Is the 9H-fluoren-9-ylium cation aromatic?

In this cation, there are two individual benzene rings which are aromatic. But in the entire π system, there are 12 π-electrons which should make it antiromatic. Which is correct?
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0answers
18 views

How does mesh size of Barium Chloride affect sulfate results via turbidimetric method?

I am analyzing sulfate using Standard Methods 4500 $\ce{SO4 ^2-}$ E (turbidimetric method) using $\ce{BaCl2}$ and measuring %T at 420 nm. In the past, we used an appropriate 20-30 mesh size for the $\...
7
votes
1answer
228 views

Can Le Chatelier's principle be derived?

Le Chatelier's principle says : If a constraint (such as a change in pressure, temperature, or concentration of a reactant) is applied to a system in equilibrium, the equilibrium will shift so as ...
2
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0answers
25 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) ...
11
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2answers
636 views

Is the notion of orbitals different in theoretical chemistry?

I am just an average chemistry student that is currently exposed to theoretical chemistry. And I am seeing very puzzling things, such as 1p, 2f, 3g orbitals. In my attempt to reconcile this, I was ...
7
votes
1answer
275 views

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 ...
4
votes
1answer
360 views

How to explain the excited states in the dinitrogen cation?

The $\ce{N2^+}$ molecule has the molecular orbitals $$\ce{\sigma(1s)^2\; \sigma^*(1s)^2\; \sigma(2s)^2\; \sigma^*(2s)^2\; \pi(2p_x)^2 \; \pi(2p_y)^2 \; \sigma(2p_z)^1,}$$ which can be seen on the ...
10
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1answer
258 views

What exactly is meant by 'multi-configurational' and 'multireference'?

Some topics here have touched on this before (see 1, 2, 3), but I haven't found a clear definition yet. I would like to know what exact property of the wave function these terms refer to. It would ...
7
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1answer
172 views

Is the Lowdin Orthogonalization used in diagonalizing the atomic orbitals really a basis change?

This is kind of more on the mathematics side of quantum chemistry, but I can't quite figure out why the Lowdin Orthogonalization is called a basis set change. I get how it works from the perspective ...
2
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0answers
147 views

What studies show that d orbitals don't play an important role in covalent bonding? (> period 2 elements) [closed]

Take a look at all the following molecules: $\ce{SO3^{2-}}$, $\ce{SO2}$, $\ce{SO4^2-}$, $\ce{PF5}$ and many more you can add. In all these there is a controversy of one of these two types: Is formal ...
12
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5answers
631 views

Visualizing atoms in XYZ file with colors representing partial charges

I have a file containing the atomic coordinates (in XYZ format) of a structure, and I also have a list of the partial atomic charges for each atom. I'd like to create an image of the structure where ...
4
votes
0answers
79 views

Number of configurations/states for electrons in orbitals

I'm performing complete active space calculations for the prediction of X-ray absorption L edge spectra. This involves an excitation from 2p orbitals to the 3d orbitals of the metal. For the ...
5
votes
1answer
111 views

How are the LCAO ansatz and Slater determinant ansatz for the wavefunction connected?

Say we have a system of 2 electrons, an ansatz for the wavefunction is then a Slater determinant consisting of two orbitals. $$ \left|\Psi_{Slater}\right>= \frac{1}{\sqrt{2!}}\left(\left|\phi_1\...
8
votes
3answers
273 views

What is Nesbet's theorem?

In a talk by Frank Neese there was a slide with title "Nesbet's theorem" and an equation indicating something like "if your wavefunction has the double excitation amplitudes correct, then you can get ...
6
votes
1answer
647 views

Why can't NH5 form?

In ammonia a nitrogen atom forms 3 covalent bonds with hydrogen atoms and has one lone pair which can be used in a dative covalent bond with another hydrogen atom to form an ammonium ion. Instead of ...
5
votes
1answer
126 views

Detail from Integral Evaluation in Szabo (Appendix)

This is a step from Appendix A in Szabo and Ostlund's Quantum Chemistry. In short, the question is how to get from \ref{A.20} to \ref{A.21}. We can factor out some constants $K$ in the expressions to ...
3
votes
1answer
126 views

What is the difference between non-adiabatic coupling and diabatic coupling?

The diabatic couplings are the off-diagonal terms of wave functions written in a diabatic basis. There is a need to use the diabatic basis when there is a breakdown of the Born-Oppenheimer ...
6
votes
1answer
134 views

How do restricted open shell calculations mathematically proceed in the context of the self consistent field iterations?

I'm specifically concerned with HF theory. I understand restricted closed shell calculations use the Roothaan equations. If I understand correctly these equations assume each filled molecule orbital ...
3
votes
1answer
143 views

How are imaginary frequencies and force constant calculated by DFT?

Computational calculations allow us to simulate the frequencies of molecules. They can even tell us if the optimized structure is a minimum, a saddle point or a maximum according to the number of ...
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0answers
145 views

The nature of Chemical Bonds [closed]

It was nearly a year ago when I appeared for my first interview through the KVPY (a research oriented scholarship exam) when one of the questions the panel asked me was : What is a chemical bond? ...
2
votes
1answer
73 views

Franck-Condon factors in photoelectron spectroscopy

Franck-Condon factors have been used to predict / assign the vibrational structure of photo-electron spectra. $FCF=|\langle\psi''_{vib}|\psi'_{vib}\rangle|^2 = |\langle\psi''_{vib,1}\psi''_{vib,2},\...
2
votes
1answer
130 views

How to know about radical character of a diradical molecule?

I understand that the radical character is quantified by the occupation number of the lowest unoccupied natural orbital obtained from UHF calculations or from CASSCF calculations. My issue is that I ...
5
votes
0answers
98 views

Why is spin-contamination undesirable?

Why is spin-contamination, introduced by e.g. Unrestricted Hartree Fock, undesirable, and to which problems further on can it lead? The only problem I currently see myself is that spin-contamined ...
10
votes
1answer
215 views

Why is density fitting not used to reduce four-center integrals further down to two-center integrals?

In density fitting, why don't researchers turn all the 4-center integrals into 2-center ones instead of stopping at composing them from 3-center integrals?
4
votes
1answer
127 views

Can we predict with any reliability whether a chemical is carcinogenic in people?

I know that some chemical compounds have been known to be carcinogenic in humans. But can we make a reliable prediction of how likely a substance is to be carcinogenic based on the chemical and ...