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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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33 views

How to achieve Löwdin transformation?

I use Gaussian 09 to obtain the Hamiltonian and overlap matrices, $H_0$ and $S_0,$ where the B3LYP functional and the 6-31G basis set are adopted. Then how to transform the system to an orthogonal ...
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1answer
62 views

How does resonance fail in approximating chemical structures?

In the book "Concise Inorganic Chemistry" by Prof. JD Lee, it says here: These contributing structures do not actually exist. The $\ce{CO3^2-}$ does not consist of a mixture of these structures, ...
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45 views

Is there any publicly available software that can do deterministic CCSDTQP other than MRCC?

MRCC can do arbitrary order coupled cluster but much of the code is computer-generated (not hand-coded by a human) so it can be slow. There are some stochastic codes for high-order coupled cluster, ...
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48 views

Explosive reaction based on reaction rate

Question We have the following chemical reactions: $$ \begin{align} \ce{A + B^* &-> C + D^*}\tag{1}\\ \ce{D^* &-> B^* + B^*}\tag{2}\\ \ce{B^* &-> B}\tag{3} \end{align} $$ ...
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1answer
1k views

Will Proving or Disproving of any of the following have effects on Chemistry in general?

I am working on a project relating to- https://en.wikipedia.org/wiki/Millennium_Prize_Problems I wanted to list the effects of them being proved or disproved in different aspects of science and maths....
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33 views

Psi4 gradient calculation with complete basis set? [closed]

I'm trying to set up a gradient calculation for psi4. In my input.dat file, I have tried the following keywords: set basis cc-pVTZ gradient('CCSD(T)') which is ...
5
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0answers
33 views

Why are the OV and VO blocks of the CIS 1RDM zero?

I know the reduced density matrix has the form: $$ \gamma(\alpha,\beta) = \langle\Psi_N|c^{\dagger}_{\alpha} c_{\beta}|\Psi_n \rangle $$ but when $\Psi_N$ is the configuration interaction singles (CIS)...
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2answers
106 views

Dipole moment of water using the definition [closed]

In many Chemistry books, the dipole moment of molecules is calculated through algebraic formulas. However, another definition of the dipole moment is $$\vec{\mu} = \sum_i q_i \, \vec{r}_i$$ So, how ...
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3answers
145 views

What are the effects of radio waves on matter?

Different regions of the electromagnetic spectrum interact differently with matter: Microwave radiation can induce molecular rotation. Infrared radiation can induce molecular vibration. Visible and ...
2
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0answers
69 views

What is the largest known zero-point energy for a molecule?

I was surprised to find out that the zero-point energy (ZPE) for the ground state of $\ce{BH3}$ is a few thousand $\pu{cm-1}$, because for molecules I usually work with, it's much smaller. Does anyone ...
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69 views

How to formulate the 1 dimensional time-dependent Schrodinger’s equation from a given function?

Assuming $f(t) =e^{−iωt}$, formulate the 1 dimensional time-dependent Schrodinger’s equation. I started solving the problem as \begin{align} E &= hf, \tag1\label{eq:1}\\ E &= ħw, \tag2\...
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2answers
130 views

Chaos in chemical reactions

I recently read about Chaos Theory and was wondering if a chemical reaction results in or shows characteristics of chaos (I found a few examples of such reactions here) Chaos theory concerns ...
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1answer
102 views

What is the biggest known difference between rₑ and r₀?

What is the biggest known difference between $r_e$ and $r_0$? Where $r_0$ is the average bond length of the lowest vibrational state, and $r_e$ is the location where the potential is lowest. For a ...
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1answer
96 views

Is it possible to have an allotrope of carbon as a long unbranched chain of itself?

Is it possible to have an allotrope of carbon with formula $\ce{(=C=)_n}$? Well, let's actually leave alone the separate question like from which "monomer" would one produce such a thing (can one ...
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39 views

Does the natural atomic orbital analysis result in natural electron configurations of molecules?

In my understanding, the natural atomic orbital (NAO) analysis is a method of calculation to get occupancy of electrons in center of each atoms. In other words, the result of NAO-occupancy indicates ...
12
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1answer
292 views

Is it good practise to mix double and triple zeta basis sets?

I need to compute extremely accurate single point energies using the coupled cluster method. The methods to be employed scale largely with the number of basis functions. A few basis functions may have ...
1
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1answer
59 views

Potential energy of electron density at the nucleus

Consider the hydrogen atom for simplicity. The electronic density at the nucleus is not null. The attractive potential between a small volume of electronic density $\mathrm dV$ (at position $\vec r$)...
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0answers
28 views

Applying the constant number of electrons in DFT density optimisation

(Previous related question: Finding mathematically the ground state density in DFT) I am studying the density optimisation procedure (in particular for Orbital-Free DFT) this thesis. The derivative ...
5
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1answer
88 views

Cauchy-Schwarz integral screening different inequalites

Eq. (9.12.23) in [1] states that: $$\sum_{abcd}c_{ab}c_{cd}g_{abcd}>0\tag{MEST 9.12.23}\label{91223}$$ with $c_{ab}=c_ac_b$ for $c_a$ being some distribution coefficients and $g_{abcd}$ being the ...
4
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1answer
79 views

Finding mathematically the ground state density in DFT

To find the ground state density in DFT, you set the following Lagrangian: $$L = E[\rho(\vec r)] - \mu\left(\int \rho(\vec r) \mathrm{d}\vec r - N\right)$$ While minimising with respect to the ...
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4answers
137 views

Heisenberg's uncertainity principle(HUC)

I know the mathematical form of HUC and its statement i.e.It is impossible to determine simultaneously. , the exact position and momentum of an electron. i don't know why this ...
6
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1answer
47 views

What are the constraints on the two electron integral matrix?

In semi-empirical methods, the two electron integral matrix is simplified and the entries are replaced by actual values instead of integrals to evaluate. However, while doing that, the variational ...
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0answers
50 views

Modelling the Oregonator

Assuming this is the correct place for a post like this, I need to write a piece of code to show the oscillations in the Oregonator. I have successfully done so for the Brusselator, but have been ...
6
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0answers
114 views

Where to find experimental spin-orbit coupling constants?

I am searching for experimental spin-orbit coupling constants, particularly for main group elements and Cr(0) to calculate correlation consistent Composite Approach (ccCA) energetics. This method ...
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1answer
71 views

Reaction of sulphur with calcium carbonate

Can sulphur react with calcium carbonate to form sulphur trioxide and calcium carbide, as the energy of 3(S=O) is greater than ((C=O) +2(C-O))? EDIT: i forgot to say that this is in an oxygen-free ...
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16 views

Catalyzing the breakdown of Si-O bonds

What catalysts can catalyze the breakdown of (Si-O) bond ? Can you mention some books(ebooks or hard cover) or websites that cover a lot of information about (Si-O) bond characteristics? I have ...
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1answer
50 views

Doubt on Element [duplicate]

I read the definition of element: Element consists of only one kind of atom and cannot be broken down into a simpler type of matter by either physical or chemical means. Then as per definition, $\...
9
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1answer
149 views

How to calculate the amount charge transfer from a natural population analysis?

I am trying to reproduce the quantity referred to as the degree of charge transfer reported in this publication by Zhu et al. [Ref. 1] for the F4-TCNQ molecule. I am interested in section 3.2 in the ...
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0answers
31 views

What makes determining entropy changes theoretically so hard compared to enthalpy?

It is really hard to determine the entropy change of a reaction accurately because of subtle solvent effects and a lack of standard entropies. On the other hand, enthalpy is relatively easy and ...
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0answers
105 views

Is there a reliable chemical theory that predicts pKa based on structure?

Obviously, there are general stability arguments that can be made to estimate relative pKas, such as evaluating the stability of the conjugate base of an acid, or thinking about how polarized the bond ...
6
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64 views

Do “random” “2D” polymers constrained to a box actually form “space filling” curves?

Background: The self avoiding walk model is (allegedly) a reasonable model for polymers, at least with respect to certain "universal" (i.e. lattice independent) constants -- see section 1.1. in this ...
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1answer
117 views

How to calculate S² value of a broken-symmetry wave function?

$S$ represents spin, signifies the number of unpaired electrons in the system. For example, if the number of unpaired electrons is $1$, then $S=1/2$. $S^2$ is calculated as $S(S+1)$. From what I have ...
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2answers
374 views

Kolmogorov backward equations in active biological systems

I am trying to understand the following equations from a paper by Wang et al. [1, p. 5 at the SI]: Michaelis–Menten Representation of the Kinesin Cycle We assumed that there is a strong ...
3
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0answers
41 views

Explaining hypervalency in the framework of molecular orbital theory

In preparing for teaching duties in an introductory course in inorganic chemistry, I seem to have made a digression into how we understand the hypervalent molecules. Just to re-iterate what this ...
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0answers
37 views

All possible determinants forms a complete basis [closed]

How do we mathematically prove that the set of all possible excited determinants forms a complete basis for expanding the wavefunction (as in full configuration interaction)?
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45 views

Why does a 4-bonded nitrogen atom appears negatively charged after an optimization?

I have a molecule bearing a quaternary ammonium and I optimized it using M062X (also Hartree-Fock) using basis sets 6-31G(d,p) and 6-31G+(d,p) respectively. After optimization, I expect that the ...
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0answers
30 views

Is there an easy explanation of MP2 calculation [closed]

for my master thesis I calculated some ring strains with MP2 calculation. It was not hard to calculate these things but I'm struggling to understand what the theory is about. Now I'm defending my work ...
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0answers
68 views

Variational method: Hydrogen atom ground state in STO-3G basis expansion

I computed numerically the ground state energy of hydrogen by variational procedure, firstly expanding the wave function over the s-wave basis set STO-3G $$\psi(r)=\sum_{i=0}^3 C_{i} e^{-\alpha_ir^2}$$...
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0answers
49 views

Is there a mathematical basis behind the HSAB theory?

I learnt about the HSAB concept about a year ago, and found that it helped rationalise many of the solubilities/reactivities that “pure” Lewis acid/base theory could not. Is there a mathematical ...
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0answers
65 views

Antisymmetrized Product of Strongly Orthogonal Geminal (APSG) method

To get a deeper understanding of electronic structure methods, like Hartree-Fock, MP2, and Coupled Cluster method, there are many small programs (codes) available in Python, C++ or Fortran, for ...
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0answers
119 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 ...
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2answers
92 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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119 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
57 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 ...
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1answer
35 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 ...
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1answer
233 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 ...
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2answers
121 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
135 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
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1answer
38 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
58 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 ...