This can be great for stress relief in a few ways. First, the idea of pleasures comes to mind. Pleasures are little things in life that give you a lift and make you happier. Pleasures have been studied by those in the field of positive psychology, and it's been found that they help us to not only be happier, but less stressed and more effective at what we do. (See this study by Barbara Frederickson for more on that.) If we do a few extra fun things in the course of a day, we can break up the pressure we may face, enjoy life a little more, and perhaps be more effective in our lives as well.
Second, many people find that they need some time off here and there or they get dangerously close to burnout (or find themselves fully entrenched in it). Studies show that people are happier and more relaxed on Friday nights, and more stressed during the week, which is likely due to the extra time for leisure and the freedom that comes with the weekend. We can't will ourselves extra weekend days, though, and many people go several years between vacations. Taking the time to try something new can be another route to the sense of freedom that comes with a weekend or a vacation, even if the amount of is is somewhat less. It's important to have some fun in life, and trying something new for Leap Day--or any other day--can be a way to make that happen.
Finally, when we try a new challenge, we often find that we have strengths we didn't know we had. "Leaping" into something new--maybe something you've been wanting to do but waiting for the right time--can introduce you to new areas at which you may excel. This can boost your confidence in other areas of life and raise self-esteem. What does this have to do with stress? We tend to feel less stressed when we know we have the inner resources to handle what we face in life; having a stronger sense of self-efficacy (and an internal locus of control) can lead to more feelings of confidence and a reduced sense of stress.
For these reasons, I think the idea of 'taking that leap' is important for us to remember more often than once every four years. However, because Leap Day is upon us, there's no time like the present.
How can you make your Leap Day work for you?
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