diff --git a/README.md b/README.md index 1bbcb40..4e1df08 100644 --- a/README.md +++ b/README.md @@ -159,13 +159,13 @@ the PSI4 VQM24 dataset: python scripts/validate_vqm24.py ``` -Validate zero-point energies across 255 model chemistries: +Run a zero-point-energy regression across 255 model chemistries: ```bash python scripts/validate_model_chemistry_zpe.py ``` -Validate complete DFTB+ and GFN2-xTB entropy workflows against an experimental +Compare complete DFTB+ and GFN2-xTB entropy workflows with an experimental gas-phase compilation: ```bash diff --git a/docs/benchmarks/entropy_accuracy.rst b/docs/benchmarks/entropy_accuracy.rst index 23cc705..002de83 100644 --- a/docs/benchmarks/entropy_accuracy.rst +++ b/docs/benchmarks/entropy_accuracy.rst @@ -21,8 +21,10 @@ low-frequency torsions. For each molecule, the reference value is the median of the available experimental columns in the workbook. This avoids selecting a single transcription when the compilation contains conflicting entries, as it does -for methane. Nitric oxide is the documented exception: its two entries differ -by almost 10 J/(mol K), so the JANAF value is used. Values are converted from +for methane. The source publication states that radicals were excluded from +the curated entropy set, although the workbook contains nitric oxide. It is +included here only as an open-shell stress case. Its two entries differ by +almost 10 J/(mol K), so the JANAF value is used. Values are converted from J/(mol K) to cal/(mol K). Both engines start from the corresponding ASE G2 geometry and run a complete @@ -40,7 +42,7 @@ DFTB+ and the 3ob parameter set are required for the default run: python scripts/validate_experimental_entropy.py -Run both independently implemented engines with: +Run both electronic-structure engines with: .. code-block:: bash @@ -71,6 +73,8 @@ Results All deviations are in cal/(mol K). The regression gate requires an MAE no greater than 0.75 and a maximum deviation no greater than 3.0 cal/(mol K). +These limits preserve the behavior of this selected molecular set; they are +not general accuracy criteria for other chemical spaces. Interpretation -------------- @@ -82,6 +86,11 @@ accuracy limits of DFTB3/3ob and GFN2-xTB and are not numerical errors in the thermochemistry formulas. Those formulas are separately tested against ASE ``IdealGasThermo``. +DFTB+ and GFN2-xTB independently generate the optimized geometries and +frequencies, but both feed the same ThermoScreening thermochemistry +implementation. Agreement between the engines therefore does not constitute +an independent validation of those shared formulas. + The source workbook is not redistributed. See the `dataset publication `__ for provenance, experimental-source details, and limitations.