BACKGROUND: THE “MODERN IONIC LIQUIDS” DESCRIBED IN THE FIRST ARTICLE IN THIS ISSUE BY KEITH JOHNSON HAVE CERTAINLY CAPTURED THE IMAGINATION OF CHEMISTS ACROSS THE GLOBE, AND WITHOUT AT DOUBT, NOWHERE MORE THAN IN SYNTHESIS AND CATALYSIS. [1] THE REASONS FOR SUCH PHENOMENAL INTEREST IN THIS AREA ARE DUE TO SEVERAL FACTORS, NOTABLY: [2]METHODS: ALL THE STRUCTURES STUDIED IN THIS WORK WERE FULLY OPTIMIZED, WITHOUT SYMMETRY RESTRICTIONS USING B3LYP AND HF METHODS IN CONJUNCTION WITH 6-31+G* AND 6-311++G** BASIS SETS. ALL CALCULATIONS WERE PERFORMED USING THE GAUSSIAN 09 PROGRAM PACKAGE.RESULTS: IN ORDER TO FIND THE MOST STABLE CONFIGURATION OF ION PAIR [THIAZOLIUM]+[A]-, (A=F-, CL-, BR-, CLO4-, CH3COO-, CF3-, C6H5CO2-, NO3-, ... FIRST THE MOST STABLE CONFORMER OF ANION AND CATION WERE OBTAINED. THEN THESE ANIONS WERE ARRANGED AROUND THE CATION IN "CHEMICALLY INTUITIVE" POSITIONS WHERE INTERACTION WITH HYDROGEN ATOMS OF THE CATION IS A POSSIBILITY. FINALLY FIVE STABLE CONFIGURATIONS WERE LOCATED SO THAT THEIR STRUCTURES ARE FULLY OPTIMIZED BY THE B3LYP AND HF METHODS WITH DIFFERENT BASIS SETS.CONCLUSION: CALCULATION OF BINDING ENERGY SHOW THAT ALL VALUES ARE NEGATIVE, THEREFORE, THERE IS A TENDENCY BETWEEN CATION AND ANION FOR FORMATION IONIC LIQUIDS. THE CHARGE ON ATOMS IS DIFFERENT BEFORE AND AFTER INTERACTION BETWEEN CATION AND ANION. THE CALCULATION BY USING TWO METHODS HF AND B3LYP ARE CONCLUDED THE SAME TRENDS. ALTHOUGH, EXPERIMENTAL METHODS HAVE PROVIDED A LOT OF INFORMATION ABOUT THE AGGREGATION CHARACTERISTICS OF ILS, IT IS STILL A GREAT CHALLENGE TO UNDERSTAND THE BEHAVIOURS OF THESE ILS AT MOLECULAR LEVELS.