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In Gaussian calculations, a negative or imaginary frequency usually indicates an unstable geometry or transition state. In Gaussian calculations, frequencies are computed to determine whether a given geometry corresponds to a minimum on the potential energy surface (stable structure) or a transition state (stationary point along a reaction pathway).
When performing a frequency calculation, Gaussian calculates the second derivatives of the energy with respect to the nuclear coordinates to obtain the force constants and then solves the resulting eigenvalue problem. The eigenvalues represent the vibrational frequencies of the system.
A positive frequency indicates a normal mode of vibration, corresponding to a stable structure. These vibrations involve the atoms oscillating around their equilibrium positions.
On the other hand, a negative frequency indicates an imaginary mode of vibration. It suggests that the energy is increasing in that direction, meaning the structure is unstable. An imaginary frequency usually arises when the geometry corresponds to a transition state, which is a saddle point on the potential energy surface. Transition states connect reactant and product molecules in a chemical reaction.
It's important to note that Gaussian calculations are subject to certain approximations and limitations. In some cases, a small negative frequency may be obtained due to numerical noise or insufficient convergence rather than indicating a truly unstable structure. Therefore, it's essential to carefully analyze the results, consider convergence criteria, and verify the nature of the negative or imaginary frequency through further calculations or analysis.
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When dealing with negative frequencies in Gaussian calculations, there are a few steps you can take to address the issue:
Check convergence: Ensure that the frequency calculation has properly converged. Insufficient convergence can sometimes lead to spurious or inaccurate results. Verify that the optimization and frequency calculations have reached a satisfactory level of convergence, typically by checking the root-mean-square (RMS) gradient and displacement values.
Verify the nature of the negative frequency: Confirm whether the negative frequency corresponds to a true instability or if it is an artifact of the calculation. One way to do this is by analyzing the corresponding vibrational mode. Negative frequencies can arise due to numerical noise, insufficient convergence, or inaccuracies in the computational method. However, if the negative frequency persists even after thorough convergence checks, it likely indicates an unstable geometry or a transition state.
Perform a constrained optimization: If you suspect that the negative frequency is due to an unstable geometry, you can attempt a constrained optimization to enforce stability. Fix the positions of certain atoms or bonds that are involved in the unstable mode and optimize the remaining coordinates. This can help to modify the geometry and alleviate the instability, potentially leading to a stable structure.
Transition state search: If the negative frequency corresponds to a transition state, you can use methods specifically designed for locating transition states, such as the nudged elastic band (NEB) or the growing string method (GSM). These methods allow you to identify the reaction pathway and locate the true transition state structure.
Perform additional calculations: If you're still unsure about the nature of the negative frequency, consider performing additional calculations to validate the results. These may include using different basis sets, checking for other imaginary frequencies, or performing higher-level calculations (e.g., using density functional theory with a different functional).
Geometry Optimization
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• Geometry Optimization ...
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25 авг 2024
