Advertisement

Topics

Eliminating Systematic Errors in DFT via Connectivity-Based Hierarchy: Accurate Bond Dissociation Energies of Biodiesel Methyl Esters.

08:00 EDT 15th April 2019 | BioPortfolio

Summary of "Eliminating Systematic Errors in DFT via Connectivity-Based Hierarchy: Accurate Bond Dissociation Energies of Biodiesel Methyl Esters."

We present a computational study focusing on the determination of accurate bond dissociation energies (BDEs) involved in the combustion of biodiesel methyl esters. We have adapted our previously developed efficient error-cancellation protocols, based on the systematic "connectivity-based hierarchy" (CBH), to derive accurate BDEs of biodiesel molecules at a modest computational cost. Using DFT energies on the full biodiesel molecule in conjunction with accurate G4 energies on the small fragments involved in the CBH reaction schemes, systematic errors in the DFT methods can be cancelled efficiently. Herein, we apply our G4-corrected ΔCBH-2 and ΔCBH-3 schemes in conjunction with several popular DFT methods to determine accurate bond dissociation energies of different C-C, C-H, and C-O bonds in biodiesel surrogate molecules. We first evaluate the performance of different DFT methods using a test set of 21 reactions involving various bond dissociations in small to medium biodiesel surrogates (up to methyl decanoate, a C10-methyl ester) by calibration against accurate values calculated with multireference methods (MRACPF2), reported by Carter and co-workers. The CBH-2 corrections for all tested dispersion-corrected functionals yield mean absolute deviations (MADs) in a narrow range of 1.3-1.5 kcal/mol, the best performance being obtained for B97-D3 and ωB97X-D functionals (MAD = 1.3 kcal/mol). Further, significant improvement yielding a MAD of only 0.9 kcal/mol is obtained using the G4-corrected CBH-3 scheme. Finally, the protocol has been applied to derive accurate BDEs of eight different bonds in the larger biodiesel molecule, methyl linolenate, yielding a MAD of only 1.13 kcal/mol using the ΔCBH-3 error correction scheme. The results suggest that our protocol in conjunction with different DFT methods should be broadly applicable to yield accurate BDEs for a variety of large biodiesel molecules.

Affiliation

Journal Details

This article was published in the following journal.

Name: The journal of physical chemistry. A
ISSN: 1520-5215
Pages:

Links

DeepDyve research library

PubMed Articles [22849 Associated PubMed Articles listed on BioPortfolio]

Experimental Design in Quantitative Proteomics.

Metabolites and proteins are potential biomarkers. They can be identified with the help of mass spectrometry (MS). However, measurements obtained by using MS are prone to various random and systematic...

Turning vice into virtue: Using Batch-Effects to Detect Errors in Large Genomic Datasets.

It is often unavoidable to combine data from different sequencing centers or sequencing platforms when compiling datasets with a large number of individuals. However, the different data are likely to ...

Visuo-Proprioceptive Matching Errors Are Consistent with Biases in Distance Judgments.

People make systematic errors when matching the location of an unseen index finger with that of a visual target. These errors are consistent over time, but idiosyncratic and surprisingly task-specific...

Image-based analysis of uniaxial ring test for mechanical characterization of soft materials and biological tissues.

Uniaxial ring test is a widely used mechanical characterization method for a variety of materials, from industrial elastomers to biological materials. Here we show that the combination of local materi...

Do pupil-based binocular video eye trackers reliably measure vergence?

A binocular eye tracker needs to be accurate to enable the determination of vergence, distance to the binocular fixation point and fixation disparity. These measures are useful in e.g. the research fi...

Clinical Trials [4982 Associated Clinical Trials listed on BioPortfolio]

Improving Parental Understanding of Medication Instructions Through a Pictogram-Based Intervention

Liquid medication administration errors are common, and place children at risk for adverse events. Caregivers with low socioeconomic status (SES), low education and poor health literacy s...

Outpatient Prescription Errors: Detection, Analysis, and Impact on Safety

The purpose of this study is to better understand outpatient prescribing errors through clinic and pharmacy-based error reporting systems.

Validation of Brief Objective Neurobehavioral Detectors (BOND) in Mild TBI

The Veterans Health Administration (VHA) has stated the need for a brief screening instrument that can assist with the triage of the enormous number of returning OEF/OIF veterans with conc...

Work Hour Reductions, Medical Errors, and Intern Well-Being at Providence St. Vincent Medical Center Intensive Care Unit

The purpose of this study is to determine whether reducing intern work hours and eliminating extended shifts in the intensive care unit will reduce prescribing errors and improve intern we...

E-learning to Prevent Drug Errors in Anesthesia

The purpose of this observational study is to assess the efficiency of an e-learning in order to put into practice some preventive measures to avoid medication errors during anesthesia.

Medical and Biotech [MESH] Definitions

Errors or mistakes committed by health professionals which result in harm to the patient. They include errors in diagnosis (DIAGNOSTIC ERRORS), errors in the administration of drugs and other medications (MEDICATION ERRORS), errors in the performance of surgical procedures, in the use of other types of therapy, in the use of equipment, and in the interpretation of laboratory findings. Medical errors are differentiated from MALPRACTICE in that the former are regarded as honest mistakes or accidents while the latter is the result of negligence, reprehensible ignorance, or criminal intent.

Individuals connecting by family, work or other interests. It also includes connectivity facilitated by computer-based communications.

A measure of PATIENT SAFETY considering errors or mistakes which result in harm to the patient. They include errors in the administration of drugs and other medications (MEDICATION ERRORS), errors in the performance of procedures or the use of other types of therapy, in the use of equipment, and in the interpretation of laboratory findings and preventable accidents involving patients.

The formal process of obtaining a complete and accurate list of each patient's current home medications including name, dosage, frequency, and route of administration, and comparing admission, transfer, and/or discharge medication orders to that list. The reconciliation is done to avoid medication errors.

Any deviation of results or inferences from the truth, or processes leading to such deviation. Bias can result from several sources: one-sided or systematic variations in measurement from the true value (systematic error); flaws in study design; deviation of inferences, interpretations, or analyses based on flawed data or data collection; etc. There is no sense of prejudice or subjectivity implied in the assessment of bias under these conditions.

Advertisement
Quick Search
Advertisement
Advertisement

 


DeepDyve research library

Searches Linking to this Article